WO2022172962A1 - 樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス、並びに、環化樹脂の前駆体 - Google Patents
樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス、並びに、環化樹脂の前駆体 Download PDFInfo
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- DCFYRBLFVWYBIJ-UHFFFAOYSA-M tetraoctylazanium;hydroxide Chemical compound [OH-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC DCFYRBLFVWYBIJ-UHFFFAOYSA-M 0.000 description 1
- JVOPCCBEQRRLOJ-UHFFFAOYSA-M tetrapentylazanium;hydroxide Chemical compound [OH-].CCCCC[N+](CCCCC)(CCCCC)CCCCC JVOPCCBEQRRLOJ-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
Definitions
- the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a semiconductor device, and a precursor of a cyclized resin.
- Cyclized resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulating properties.
- the use is not particularly limited, but in the case of a semiconductor device for mounting, use as a material for an insulating film or a sealing material, or as a protective film can be mentioned. It is also used as a base film or coverlay for flexible substrates.
- the cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin.
- a resin composition is applied to a substrate, for example, by coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
- a precursor of the cyclized resin such as a polyimide precursor is cyclized, for example, by heating, and becomes a cyclized resin such as polyimide in the cured product. Since the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc.
- Patent Document 1 discloses a polymer precursor whose reaction to a final product is promoted by a basic substance or by heating in the presence of a basic substance, and A photosensitive resin composition is described that contains a base generator that generates a base upon irradiation and heating.
- Patent Document 2 describes a resin composition containing the following components (a) to (d).
- (a) Polyimide precursor having a specific structural unit (b) Compound that generates radicals upon exposure to actinic rays (c) Compound having a specific structure (d) Solvent
- a resin composition containing a precursor of a cyclized resin is patterned by exposure, development, or the like, and then the precursor of the cyclized resin is cyclized to obtain a pattern of a cured product.
- the pattern of the cured product is required to be excellent in rectangularity.
- the pattern of the cured product has excellent rectangularity, and the taper angle between the side surface of the cured product and the substrate on which the cured product is formed does not exceed 90 °, and the cross-sectional shape of the pattern is not a constricted shape. , means that the taper angle is close to 90°.
- excellent in the rectangularity of the cured product is also simply referred to as "excellent in the rectangularity of the cured product".
- the present invention provides a resin composition having excellent rectangularity of a cured product obtained, a cured product obtained by curing the resin composition, a laminate containing the cured product, a semiconductor device containing the cured product or the laminate, and
- An object of the present invention is to provide a method for producing a cured product by which a cured product having excellent rectangularity can be obtained, and a precursor of a novel cyclized resin.
- a resin composition comprising a precursor of a cyclized resin, wherein the precursor of the cyclized resin is a precursor of the cyclized resin that generates a base when heated to 250°C.
- ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the structure exhibiting the property of generating a base contained in the precursor of the cyclized resin contains an amide bond.
- ⁇ 5> The resin composition according to ⁇ 4>, wherein the amide bond is bonded to the main chain of the precursor of the cyclized resin on the carbonyl group side.
- ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the precursor of the cyclized resin contains a structure represented by the following formula (1-1).
- each R 1 is independently a hydrogen atom or a monovalent organic group, two R 1s may be linked to form a ring structure, and L 1 is a trivalent organic represents a group, and * represents a binding site with another structure.
- ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a base generator.
- ⁇ 10> The resin composition according to any one of ⁇ 1> to ⁇ 9>, which is used for forming an interlayer insulating film for a rewiring layer.
- ⁇ 11> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 10>.
- ⁇ 12> A laminate comprising two or more layers made of the cured product according to ⁇ 11> and a metal layer between any of the layers made of the cured product.
- ⁇ 13> A semiconductor device comprising the cured product according to ⁇ 11> or the laminate according to ⁇ 12>.
- the method for producing a cured product according to ⁇ 14> wherein the ratio F/E of the number of moles F of the generating group exceeds 0.9.
- the ratio X/Y of the concentration X of the base generating group in the upper 50% of the thickness direction of the film to the concentration Y of the base generating group in the lower 50% of the film is 0.5%.
- Precursors of cyclized resins containing repeating units of In formula (2) 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
- at least one of R 111 , R 115 , R 113 and R 114 is represented by the following formula (1-1) Including structure.
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. and at least one of R 121 , R 122 , R 123 and R 124 includes a structure represented by the following formula (1-1).
- 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 a monovalent and at least one of R 117 , R 111 and R 113 includes a structure represented by the following formula (1-1).
- each R 1 is independently a hydrogen atom or a monovalent organic group
- two R 1s may be linked to form a ring structure
- L 1 is a trivalent organic represents a group
- * represents a binding site with another structure.
- a resin composition having excellent rectangularity in a cured product obtained, a cured product obtained by curing the resin composition, a laminate containing the cured product, and a semiconductor device containing the cured product or the laminate , and a method for producing a cured product with which a cured product having excellent rectangularity is obtained, and a precursor of a novel cyclized resin are provided.
- a numerical range represented by the symbol "to” means a range including the numerical values before and after "to” as lower and upper limits, respectively.
- the term "process” is meant to include not only independent processes but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
- a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
- an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified.
- Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
- (meth)acrylate means both or either of “acrylate” and “methacrylate”
- (meth)acrylic means both “acrylic” and “methacrylic”
- (meth)acryloyl means either or both of “acryloyl” and “methacryloyl”.
- Me in the structural formulas represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- total solid content refers to the total mass of all 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 number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by connecting Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) in series. Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent.
- THF tetrahydrofuran
- NMP N-methyl-2-pyrrolidone
- detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm unless otherwise specified.
- UV ray ultraviolet
- the positional relationship of each layer constituting the laminate is described as "above” or “below”, it means that another layer is above or below the reference layer among the layers of interest. It would be nice if there was That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
- the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as “upper”. and the opposite direction is called “down”.
- the composition may contain two or more compounds corresponding to each component contained in the composition.
- the content of each component in the composition means the total content of all compounds corresponding to that component.
- the temperature is 23° C.
- the pressure is 101,325 Pa (1 atm)
- the relative humidity is 50% RH, unless otherwise stated. Combinations of preferred aspects are more preferred aspects herein.
- the resin composition of the present invention contains a cyclized resin precursor, and the cyclized resin precursor is a cyclized resin precursor that generates a base when heated to 250°C.
- a resin that is a precursor of a cyclized resin and generates a base when heated to 250° C. is also referred to as a “specific resin”.
- the specific resin preferably generates a base by heating at 220°C, more preferably exhibits the property of generating a base by heating at 200°C, and further preferably generates a base by heating at 190°C. It is particularly preferred to generate the base by heating at 180°C.
- the lower limit of the temperature at which the base is generated is not particularly limited, it is preferably 100° C. or higher from the viewpoint of the storage stability of the composition.
- the resin composition of the present invention is preferably used for forming a photosensitive film subjected to exposure and development, and is preferably used for forming a film subjected to exposure and development using a developer containing an organic solvent.
- the resin composition of the present invention can be used, for example, to form an insulating film for semiconductor devices, an interlayer insulating film for rewiring layers, a stress buffer film, and the like, and can be used to form an interlayer insulating film for rewiring layers. preferable.
- the resin composition of the present invention may be used for forming a photosensitive film for positive development, or may be used for forming a photosensitive film for negative development.
- negative development refers to development in which non-exposed areas are removed by development in exposure and development
- positive development refers to development in which exposed areas are removed by development.
- the exposure method, the developer, and the development method include, for example, the exposure method described in the exposure step, the developer and the development method described in the development step in the description of the method for producing a cured product described later. is used.
- the resin composition of the present invention is excellent in the rectangularity of the obtained cured product. Although the mechanism by which the above effects are obtained is unknown, it is presumed as follows.
- Film shrinkage refers to volume reduction (shrinkage) of a cured product (eg, cured film) obtained after curing compared to the composition before curing (eg, composition film before heating).
- a cured product eg, cured film
- the composition before curing eg, composition film before heating
- a cyclized resin precursor (specific resin) that generates a base when heated to 250° C. is used as a cyclized resin precursor.
- the elution of the base generator due to development is suppressed during development, so the amount of base generated during subsequent heating is relatively large, and the elongation at break of the resulting cured product is also improved.
- the solubility in the developing solution around the aggregate is reduced at the locations where it is not aggregated (for example, the precursor of the cyclized resin). Therefore, the roughness of the pattern (for example, line edge roughness, line width roughness) may increase when the pattern is formed by development.
- the structure exhibiting the property of generating a base is distributed in a nearly uniform state over the entire film, it is presumed that the roughness can be reduced.
- Patent Documents 1 and 2 do not describe the use of specific resins.
- the resin composition of the present invention contains a cyclized resin precursor, and the cyclized resin precursor is a cyclized resin precursor that generates a base when heated to 250°C.
- the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
- the main chain represents the relatively longest connecting chain in the resin molecule.
- Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
- the precursor of the cyclized resin refers to a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin. is more preferably a resin that becomes a cyclized resin by forming a ring structure.
- Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention may contain, as the specific resin, at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. preferable.
- the resin composition of the present invention preferably contains a polyimide precursor as the specific resin.
- the specific resin generates a base when heated to 250°C. 1 mol of the resin was placed alone in a closed container, heated in the closed container under 1 atmosphere at 250° C. for 3 hours, and then quantified by HPLC (high performance liquid chromatography) to determine the amount of base generated. When 01 mol or more of base is generated, it can be determined that "a base is generated”. 1 mol of the resin, whether liquid or solid, is placed in a closed container so that the thickness is 0.50 cm or less. The amount generated is preferably 0.1 mol or more, more preferably 1 mol or more. The upper limit of the generated amount is not particularly limited, and can be, for example, 1000 mol or less.
- the base generated from the specific resin is preferably an amine, more preferably a secondary amine or a tertiary amine, and a secondary amine. is more preferred.
- the amine may be an aliphatic amine or an aromatic amine.
- the aromatic ring structure is not particularly limited, but is preferably an aromatic hydrocarbon ring structure, more preferably a benzene ring structure.
- the generated base preferably has a conjugate acid with a pKa of 0 or more, more preferably 3 or more, and more preferably 6 or more.
- the upper limit of the pKa of the conjugate acid is not particularly limited, it is preferably 30 or less.
- the pKa is 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.
- pKa is a value calculated by ACD/ChemSketch (registered trademark).
- the base generated from the specific resin is preferably liberated from the precursor of the cyclized resin during the heating.
- the base may be liberated from the cyclized resin precursor by cleavage of the base-generating site during heating, or may be liberated from the cyclized resin precursor along with ring closure of the cyclized resin precursor.
- the molecular weight of the generated base is preferably 70-500, more preferably 80-300, and even more preferably 90-220.
- the boiling point of the generated base at 1 atm is preferably 50 to 450°C, more preferably 60 to 400°C, and even more preferably 80 to 350°C.
- a specific resin in which a base remains when heated can also be used as the specific resin of the present invention.
- the generated base include, but are not limited to, the following bases. These bases may exist free in the state of these bases, or the structures of these bases from which some hydrogen atoms have been removed may exist bound to a specific resin after base generation. .
- the specific resin preferably contains a structure exhibiting the property of generating a base.
- the structure that exhibits the property of generating a base may be either an ionic structure or a nonionic structure, but from the viewpoint of the rectangularity of the resulting cured product, the nonionic structure is preferred.
- Ionic structures include quaternary ammonium cationic structures.
- Nonionic structures include structures containing amide bonds or urethane bonds.
- the specific resin preferably contains 1 to 1000 mol, more preferably 2 to 800 mol, and even more preferably 5 to 500 mol of a structure exhibiting the property of generating a base with respect to 1 mol of the specific resin. .
- the structure exhibiting the property of generating a base preferably contains an amide bond.
- the above * and # represent binding sites with other structures, respectively. In particular, both * and # are preferably bonding sites with carbon atoms.
- the substituent (R) in the substituted amide bond is not particularly limited, and a known substituent can be used, for example, an alkyl group, an aromatic hydrocarbon group, or a hydrocarbon such as a group represented by a combination thereof. groups.
- the above hydrocarbon groups may be further substituted with halogen atoms, alkoxy groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, hydroxy groups and the like. Further, the hydrocarbon group may be bonded to at least one of the nitrogen atom in the substituted amide bond and the structure bonded to the # site to form a ring structure.
- the ring structure to be formed include a piperidine ring, a morpholine ring and the like having the nitrogen atom contained in the amide bond as a ring member.
- These ring structures may further have a substituent. Examples of the substituent include the same groups as the substituents in the above hydrocarbon group.
- the amide bond in the specific resin is preferably a substituted amide bond, and a substituted amide bond having a hydrocarbon group as a substituent from the viewpoint of the generated base being highly basic and easily improving the breaking elongation. is more preferable.
- the amide bond is preferably bonded to the main chain of the precursor of the cyclized resin on the carbonyl group side. Thereby, the base generated by cleavage of the amide bond can be liberated from the specific resin.
- the specific resin preferably contains a structure represented by the following formula (1-1). Further, it is preferable that the amide group in the formula (1-1) is cleaved to generate a base during the above heating.
- each R 1 is independently a hydrogen atom or a monovalent organic group, two R 1s may be linked to form a ring structure, and L 1 is a trivalent organic represents a group, and * represents a binding site with another structure.
- each R 1 in formula (1-1) is independently a monovalent organic group.
- R 1 is preferably a hydrocarbon group, more preferably an alkyl group, an aromatic hydrocarbon group, or a group represented by a combination thereof, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 6 to 20 carbon atoms, or a group represented by a combination of these is more preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable.
- the alkyl group may be linear, branched, or cyclic.
- R 1 may have a substituent, such as a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, and a hydroxy group.
- Examples of the ring structure formed by linking two R 1 include a piperidine ring, a morpholine ring and the like having the nitrogen atom included in the above amide bond as a ring member. These ring structures may further have a substituent. Examples of the substituent include the same groups as the substituents in the above hydrocarbon group.
- R 1 examples include the structures below.
- the nitrogen atom contained in the structure of the specific example below means the nitrogen atom contained in the amide bond in formula (1-1).
- * represents a bonding site with a carbonyl group.
- a group represented by a bond with at least one structure selected from the group consisting of 2 - and -NR N - is preferred.
- RN represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.
- the hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
- saturated aliphatic hydrocarbon group a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable.
- aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and removing a plurality of hydrogen atoms from a benzene ring. group is more preferred.
- an aliphatic hydrocarbon ring group may be used as the aliphatic hydrocarbon group.
- Examples of the aliphatic hydrocarbon ring group include, but are not particularly limited to, a dicyclopentane ring, a bornene ring, an isobornene ring, or a group obtained by removing a plurality of hydrogen atoms from an adamantane ring.
- Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and removing a plurality of hydrogen atoms from a benzene ring. group is more preferred.
- the aromatic hydrocarbon group or the aliphatic hydrocarbon ring group may be condensed with another ring.
- Examples of such an embodiment include a group obtained by removing a plurality of hydrogen atoms from a phthalimide ring.
- L 1 preferably contains an aromatic hydrocarbon group as the hydrocarbon group, and contains a group obtained by removing a plurality of hydrogen atoms from a benzene ring. is more preferred.
- L 1 contains an aromatic hydrocarbon group, it is also preferred that the aromatic hydrocarbon group in L 1 is directly bonded to the hydroxy group in formula (1-1).
- the hydroxy group and the aromatic hydrocarbon group in L 1 are linked directly or via a linking group to the amide bond.
- the site where L 1 is present preferably exists at the adjacent position in the aromatic hydrocarbon group in L 1 .
- Adjacent position means that the ring member to which a certain substituent is attached in the aromatic hydrocarbon group and the ring member to which another substituent is attached are adjacent ring members in the aromatic hydrocarbon group.
- OH in formula (1-1) may be part of a carboxy group.
- the aromatic hydrocarbon group in L1 is directly bonded to the above carboxy group. Further, when the aromatic hydrocarbon group in L 1 is directly bonded to the carboxy group, the hydroxy group and the site where the aromatic hydrocarbon group in L 1 is directly or via a linking group are linked to the amide bond, It is preferably present at the adjacent position in the aromatic hydrocarbon group in L 1 .
- L 1 examples include the structures below.
- # represents the bonding site with the carbonyl group in formula (1-1), and * has the same meaning as * in formula (1-1).
- OH in the following specific examples is OH in formula (1-1).
- the specific resin preferably contains a structure represented by the following formula (1-2) as a structure exhibiting the property of generating a base.
- each R 1 independently represents a hydrogen atom or a monovalent organic group
- two R 1s may be linked to form a ring structure
- L 2 is a single bond or two represents a valence linking group
- Cy represents a ring structure
- * represents a bonding site with another structure.
- R 1 has the same definition as R 1 in formula (1-1), and preferred embodiments are also the same.
- RN is as described above.
- the hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof.
- an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable.
- the divalent aromatic hydrocarbon group includes an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a phenylene group or a naphthylene group, more preferably a phenylene group.
- Cy represents a ring structure.
- the ring structure may be either an aliphatic ring structure or an aromatic ring structure, but an aromatic ring structure is preferred. Further, it may be either a hydrocarbon ring structure or a heterocyclic ring structure, but preferably a hydrocarbon ring structure.
- the heteroatom contained in the heterocyclic structure includes an oxygen atom, a sulfur atom, a nitrogen atom, and the like.
- the heterocyclic structure includes aromatic heterocyclic structures such as pyrrole, indole, furan, benzofuran, thiophene, and benzothiophene.
- Cy preferably has an aliphatic hydrocarbon ring structure or an aromatic hydrocarbon ring structure from the viewpoint of base generation efficiency.
- the aliphatic hydrocarbon ring structure include a dicyclopentane ring, bornene ring, isobornene ring, and adamantane ring, and a dicyclopentane ring is preferred.
- the aromatic hydrocarbon ring structure is preferably an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, more preferably a benzene ring structure or a naphthalene ring structure, and still more preferably a benzene ring structure.
- the aromatic hydrocarbon ring structure or the aliphatic hydrocarbon ring structure may be condensed with another ring.
- Cy preferably has a dicyclopentane ring structure or a benzene ring structure, more preferably a benzene ring structure.
- Cy may have a substituent.
- the bonding position of Cy to the hydroxy group in formula ( 1-2 ) is Adjacent positions are preferred.
- Cy when Cy is a benzene ring, it preferably has a hydroxy group in formula ( 1-2 ) ortho to L2.
- OH in formula (1-2) may be part of a carboxy group.
- the aromatic hydrocarbon group in Cy is directly bonded to the carboxy group, the bonding position of Cy to the carboxy group is preferably adjacent to L2 in Cy.
- the specific resin preferably contains a structure represented by the following formula (1-3) as a structure exhibiting the property of generating a base.
- R 1 is a hydrogen atom or a monovalent organic group
- R 3 is a divalent organic group
- L 3 is a divalent organic group
- R 1 and L 3 are may be linked to form a ring structure
- * represents a binding site with another structure.
- R 1 has the same definition as R 1 in formula (1-1) above, and preferred embodiments are also the same.
- a group represented by a bond with at least one structure selected from the group consisting of 2 - and -NR N - is preferred.
- RN is as described above.
- the hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
- the saturated aliphatic hydrocarbon group a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable.
- the aromatic hydrocarbon group examples include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and removing a plurality of hydrogen atoms from a benzene ring. group is more preferred.
- an aliphatic hydrocarbon ring group may be used.
- the aliphatic hydrocarbon ring group include, but are not particularly limited to, a dicyclopentane ring, a bornene ring, an isobornene ring, or a group obtained by removing a plurality of hydrogen atoms from an adamantane ring.
- aromatic hydrocarbon group examples include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and removing a plurality of hydrogen atoms from a benzene ring. group is more preferred.
- the aromatic hydrocarbon group or the aliphatic hydrocarbon ring group may be condensed with another ring. Examples of such an embodiment include a group obtained by removing a plurality of hydrogen atoms from a phthalimide ring.
- R 3 preferably contains an aromatic hydrocarbon group as the hydrocarbon group, and contains a group obtained by removing a plurality of hydrogen atoms from a benzene ring. is more preferred. From the viewpoint of base generation efficiency, when R 3 contains an aromatic hydrocarbon group, it is also preferred that the aromatic hydrocarbon group in R 3 is directly bonded to the hydroxy group in formula (1-3). When the aromatic hydrocarbon group for R 3 is directly bonded to the hydroxy group in formula (1-3), the hydroxy group and the aromatic hydrocarbon group for R 3 are linked directly or via a linking group to the amide bond. The site where R 3 is preferably located adjacent to the aromatic hydrocarbon group in R 3 .
- Adjacent position means that the ring member to which a certain substituent is attached in the aromatic hydrocarbon group and the ring member to which another substituent is attached are adjacent ring members in the aromatic hydrocarbon group.
- the aromatic hydrocarbon group is a benzene ring, it means that it is in the ortho position.
- OH in formula (1-3) may be part of a carboxy group. In that case, it is also preferred that the aromatic hydrocarbon group in R 3 is directly bonded to the above carboxy group.
- the aromatic hydrocarbon group for R 3 is directly bonded to the carboxy group, the hydroxy group and the site where the aromatic hydrocarbon group for R 3 is directly or via a linking group are linked to the amide bond, It is preferably present at the adjacent position on the aromatic hydrocarbon group for R 3 .
- L 3 is not particularly limited, but is preferably a hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
- a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group represented by a combination thereof is more preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms Hydrocarbon radicals are particularly preferred.
- L3 may have a substituent , and examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, and a hydroxy group.
- the ring structure formed by linking R 1 and L 3 includes, for example, a piperidine ring, a morpholine ring and the like having the nitrogen atom contained in the above amide bond as a ring member. These ring structures may further have a substituent. Examples of the substituent include the same groups as the substituents in the above hydrocarbon group.
- R 1 represents a hydrogen atom or a monovalent organic group
- each R 4 independently represents a hydrogen atom or a monovalent organic group
- all of R 4 are hydrogen atoms.
- any one of R 1 and R 4 contains a binding site to another structure.
- R 1 when R 1 does not contain a binding site with another structure, R 1 has the same definition as R 1 in formula (1-1), and preferred embodiments are also the same.
- R 1 when R 1 contains a binding site with another structure, R 1 has the same definition as L 3 and the binding site (*) in formula (1-3), and preferred embodiments are the same.
- R 4 when R 4 does not contain a bonding site with another structure, R 4 is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 3 is more preferred), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, 6 to 10 are more preferred), arylalkyl groups (having preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms) are preferred, and a hydrogen atom or a methyl group is more preferred.
- R 4 is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 3 is more preferred), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), an
- R 4 when R 4 contains a bonding site with another structure, R 4 is an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms) , an alkenylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10 preferred), or a group represented by these bonds, and an alkylene group is more preferred.
- each R 5 independently represents a monovalent organic group, any one of R 5 contains a binding site to another structure, and A is a counter anion having a valence of 1 or more.
- each of R 5 that does not contain a bonding site with another structure preferably independently represents a hydrocarbon group.
- a hydrocarbon group an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, 2 to 3 are more preferred), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), arylalkyl groups (preferably 7 to 23 carbon atoms, preferably 7 to 19 7 to 11 are more preferred), an alkyl group is more preferred, and a methyl group is even more preferred.
- A represents a counter anion.
- A is preferably an anion with a pKa1 of 0-4.
- A is preferably a carboxylate anion, a phenol anion, a phosphate anion or a sulfate anion, and more preferably a carboxylate anion for the reason that both salt stability and thermal decomposability can be achieved.
- the carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid.
- the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less.
- the pKa1 is more preferably 3.5 or less, even more preferably 3.2 or less. According to this aspect, the stability of the resin composition can be further improved.
- pKa1 represents the logarithm of the reciprocal of the first dissociation constant of acid, and is described in Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, eds: Braude, E. A., Nachod, F.
- the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
- the resin composition of the present invention preferably contains a radical polymerization initiator described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred.
- a sensitizer described later can be included.
- a negative photosensitive film is formed from the resin composition of the present invention.
- the specific resin may have a polarity conversion group such as an acid-decomposable group.
- the resin composition of the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition of the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
- polyimide precursor Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
- 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.
- the specific resin when the specific resin contains the repeating unit represented by formula (2), the specific resin preferably contains a structure exhibiting the property of generating a base within the repeating unit represented by formula (2). ) contains the structure represented by the above formula (1-1) in the repeating unit. For example, a structure ( preferably , formula ( 1-1 ), and a structure ( preferably , It is more preferable to include a structure represented by formula (1-1). Further, when the specific resin contains a repeating unit represented by formula (2), the specific resin may contain a structure exhibiting the property of generating a base at a location different from the repeating unit represented by formula (2). .
- an aspect including a structure exhibiting a base-generating property at the end of a specific resin, a structure in which the specific resin is a repeating unit different from the repeating unit represented by formula (2) and exhibits a base-generating property
- Examples further include a repeating unit containing the above.
- a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
- R 111 in formula (2) represents a divalent organic group.
- divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
- the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the ring member hydrocarbon group is a hetero atom.
- may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred.
- Ar is each independently an aromatic group
- L is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.
- R 111 is preferably derived from a diamine.
- Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
- * represents a binding site with other structures.
- diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3, 3,3
- diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
- diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are preferably used.
- R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film.
- Ar is each independently an aromatic group
- L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO 2 — or —NHCO—, or a group consisting of a combination of two or more of the above.
- Ar is preferably a phenylene group
- L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
- the aliphatic hydrocarbon group here is preferably an alkylene group.
- R 111 is preferably a divalent organic group represented by the following formula (51) or (61).
- a divalent organic group represented by Formula (61) is more preferable.
- Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
- the monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
- R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a bonding site to the nitrogen atom in formula (2) show.
- Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
- R 115 in formula (2) represents a tetravalent organic group.
- a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
- each * independently represents a binding site to another structure.
- R 112 is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, —O—, -CO-, -S-, -SO 2 -, and -NHCO-, and preferably a group selected from a combination thereof, having 1 to 1 carbon atoms optionally substituted by a single bond or a fluorine atom 3 alkylene group, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, -C( It is more preferably a divalent group selected from the group consisting of CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
- R 111 can also contain a structure exhibiting the property of generating a base.
- R 111 preferably has a structure represented by the following formula (LD-1).
- LD-1 Y D1 represents an n+2 valent organic group
- P D1 represents a group containing a structure exhibiting the property of generating a base
- n represents an integer of 1 or more
- * It represents the binding site with the nitrogen atom to which R 111 in formula (2) binds.
- Y D1 is preferably an n+2 valent organic group, more preferably an n+2 valent organic group containing an aromatic hydrocarbon group.
- the aromatic hydrocarbon group for Y D1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and 2 or more from the benzene ring. is more preferably a group in which a hydrogen atom is removed, and a group in which 3 or more hydrogen atoms are removed from a benzene ring is particularly preferred.
- LD-1 those that directly bind to the binding sites with *, which are the two binding sites described in formula (LD-1), in Y D1 are both aromatic hydrocarbon groups. preferable. That is, the two * in formula (LD-1) are preferably directly bonded to the aromatic hydrocarbon ring structure contained in YD1 . Further, in formula (LD-1), all of the bonding sites with P D1 in Y D1 are preferably aromatic hydrocarbon groups. That is, P D1 is preferably directly bonded to the aromatic hydrocarbon ring structure contained in Y D1 .
- Y D1 preferably contains at least one structure selected from the group consisting of structures represented by the following formulas (A2-1) to (A2-5), and the above formulas (A2-1) to It is more preferably at least one structure selected from the group consisting of structures represented by formula (A2-5).
- R A211 to R A214 , R A221 to R A224 , R A231 to R A238 , R A241 to R A248 and R A251 to R A258 are each independently a hydrogen atom; , an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxy group, a cyano group, a halogenated alkyl group, or a halogen atom, and L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent represents a saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or a halogenated alkylene group, and at least one of R A211 to R A214 and at least R A221 to R A224 1, at least one of R A231 to R A238 , at least one of
- Y 1 preferably includes a structure represented by any one of formulas (A2-1) to (A2-4), and formula (A2-1) or formula ( It is more preferable to include a structure represented by any one of A2-4).
- At least one of A258 is preferably a binding site for P D1 in the above formula (LD-1).
- R A211 to R A214 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 12 carbon atoms.
- a cyclic alkyl group, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom from the viewpoint of solvent solubility, hydrogen An atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogenated alkyl group having 1 to 3 carbon atoms are more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms are more preferable.
- the halogen atom in the halogenated alkyl group in R A211 to R A214 or the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.
- R A221 to R A224 have the same meanings as R A211 to R A214 in formula (A2-1), respectively, and preferred embodiments are also the same.
- R A231 to R A238 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom.
- a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a An alkoxy group having 6 carbon atoms or a halogenated alkyl group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable.
- the halogen atom in the halogenated alkyl group in R A231 to R A238 or the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.
- L A231 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, —O—, —S -, -NR N -, a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms, preferably a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group is preferred, and a single bond or -O- is more preferred.
- the above RN is as described above.
- the divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group.
- heterocyclic group for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring is preferable, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring is preferable, a pyrrolidine ring, A group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, or a morpholine ring is more preferred.
- heterocycles may further form a condensed ring with another heterocycle or hydrocarbon ring.
- the heterocyclic ring preferably has 5 to 10 ring members, more preferably 5 or 6 members.
- the hetero atom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
- the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.
- R A241 to R A248 and L A241 have the same meanings as R A231 to R A238 and L A231 in formula (A2-3), respectively, and preferred embodiments are also the same.
- R A251 to R A258 are synonymous with R A211 to R A214 in formula (A2-1), respectively, and preferred embodiments are also the same.
- At least one of R A211 to R A214 is preferably a binding site with P D1 in formula (LD-1), and one of R A211 to R A214 is the P It is more preferably a D1 -binding site, and RA213 is preferably the above PD1 -binding site.
- at least one of R A221 to R A224 is preferably a binding site with P D1 in formula (LD-1), and one of R A221 to R A224 is the above P It is more preferably a D1 -binding site, and RA223 is preferably the above PD1 -binding site.
- R A231 to R A238 is preferably a binding site to P D1 in formula (LD-1), and two of R A231 to R A238 are the above More preferably, it is a binding site with P D1 , and more preferably, one of R A231 to R A234 and one of R A235 to R A238 are binding sites with P D1 , and R It is particularly preferred that two of A231 and RA238 are binding sites for PD1 .
- R A241 to R A248 is preferably a binding site with P D1 in formula (LD-1), and two of R A241 to R A248 are the above More preferably, it is a binding site with P D1 , and more preferably, one of R A241 to R A244 and one of R A245 to R A248 are binding sites with P D1 , and R It is particularly preferred that two of A241 and RA248 are binding sites for PD1 .
- R A251 to R A258 is preferably a binding site to P D1 in formula (LD-1), and two of R A251 to R A258 are the above More preferably, it is a binding site with P D1 , and more preferably, one of R A251 to R A254 and one of R A255 to R A258 are binding sites with P D1 , and R It is particularly preferred that two of A253 and RA257 are binding sites for PD1 .
- each of two * is preferably * in formula (LD-1). That is, the two nitrogen atoms to which R 111 in formula (2) bonds are preferably directly bonded to two positions represented by * in formulas (A2-1) to (A2-5).
- Y D1 is preferably a group represented by the following formula (Y-1) or (Y-2).
- R Y11 , R Y12 and R Y13 have the same meanings as R A211 , R A212 and R A214 in formula (A2-1), respectively, and preferred embodiments are also the same.
- R Y21 to R Y26 and L X21 have the same meanings as R A242 to R A247 and L A241 in formula (A2-4), respectively, and preferred embodiments are also the same.
- * is the binding site to the two nitrogen atoms to which R 111 in formula (2) is bound
- # is the binding site of formula (LD-1). The binding sites with PD1 in the medium are indicated, respectively.
- P D1 represents a group containing a structure exhibiting the property of generating a base described above.
- P D1 preferably has, for example, the following formula (PD-1).
- R 2 P represents a structure exhibiting the aforementioned base-generating property
- * represents a binding site with Y D1
- LP represents a divalent linking group.
- the above RN is as described above.
- Preferred embodiments of the structure exhibiting the property of generating a base are as described above. For example, the structure represented by formula (1-1), the structure represented by formula (1-2), etc. can be preferably used. .
- n represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1.
- LD-1 The structure represented by the above formula (LD-1) is obtained, for example, as a structure derived from a diamine represented by the following formula (LDA-1).
- Y D1 , P D1 and n have the same meanings as Y D1 , P D1 and n in formula (LD-1) above, and preferred embodiments are also the same.
- a resin is synthesized using a diamine having a reactive group such as a carboxyl group, and a structure (e.g., a hydroxy group, etc.) that forms a covalent bond by reacting with the reactive group and a base are generated.
- a specific resin can also be synthesized by reacting a compound having a structure that exhibits properties with the above resin.
- R 115 includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
- the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue as a structure corresponding to R115 , or may contain two or more types thereof.
- the tetracarboxylic dianhydride is preferably represented by the following formula (O).
- R 115 represents a tetravalent organic group.
- the preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
- tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride,
- tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
- R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
- R 115 can also contain a structure exhibiting a property of generating a base.
- R 115 preferably has a structure represented by the following formula (LD-2).
- LD-2 Y D2 represents an n+4 valent organic group
- P D2 represents a group containing a structure exhibiting the property of generating a base
- m represents an integer of 1 or more
- * It represents the bonding site with the carbonyl group to which R 115 in formula (2) bonds.
- Y D2 is preferably an n+4-valent organic group, more preferably an n+4-valent organic group containing an aromatic hydrocarbon group.
- the aromatic hydrocarbon group in Y D4 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and two or more from the benzene ring. is more preferably a group in which a hydrogen atom is removed, and a group in which 3 or more hydrogen atoms are removed from a benzene ring is particularly preferred.
- any of those directly bonded to the bonding site with *, which is the bonding site described in formula (LD-2), in YD2 is an aromatic hydrocarbon group. That is, the four * in formula (LD-2) are preferably directly bonded to the aromatic hydrocarbon ring structure contained in YD2 . Further, in formula (LD-2), all of the bonding sites with P D2 in Y D2 are preferably aromatic hydrocarbon groups. That is, P D2 is preferably directly bonded to the aromatic hydrocarbon ring structure contained in Y D2 .
- Y D1 preferably includes a structure represented by formula (A1-1) below, and preferably has a structure represented by formula (A1-1).
- R A11 to R A16 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxy group, a cyano group, a halogenated alkyl group, or a halogen atom
- L A11 represents a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or a halogenated alkylene group
- R A11 to R A16 At least one of or L A11 is a binding site with P D2 in the above formula (LD-2), and each * independently represents a binding site with another structure.
- R A11 to R A16 or L A11 may be a binding site with P D2 in the above formula (LD-2), but L A11 is the above-mentioned is preferably a binding site with P D2 in formula (LD-2).
- R A11 to R A16 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom.
- a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a An alkoxy group having 6 carbon atoms or a halogenated alkyl group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable.
- the halogen atom in the halogenated alkyl group in R A11 to R A16 or the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom or a bromine atom being preferred.
- L A1 is preferably a binding site to P D2 in formula (LD-2) above.
- L A1 is preferably a divalent hydrocarbon group, an aliphatic hydrocarbon group, an aromatic carbon A hydrogen group or a group represented by a combination thereof is more preferred, and an aliphatic hydrocarbon group is particularly preferred.
- the aliphatic hydrocarbon group an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable.
- L A1 is a single bond, a C 1-6 divalent saturated hydrocarbon group, a C 5-24 divalent It preferably represents an unsaturated hydrocarbon group, —O—, —S—, —NR N —, a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms, a single bond, or It preferably represents a saturated hydrocarbon group, -O- or a heterocyclic group, and more preferably represents a single bond or -O-.
- the above RN is as described above.
- -PD2- P D2 is preferably a group represented by the above formula (PD-1).
- m represents an integer of 2 or more, preferably 1 to 10, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1.
- LD-1 The structure represented by the above formula (LD-1) is obtained, for example, as a structure derived from a carboxylic acid dianhydride represented by the following formula (LDB-1).
- Y D2 , P D2 and m have the same meanings as Y D2 , P D2 and m in formula (LD-2) above, and preferred embodiments are also the same.
- the specific resin can also be synthesized by reacting the above resin with a compound having a structure exhibiting the property of generating a base.
- the method for synthesizing the specific resin can be selected in consideration of the structure of the specific resin to be obtained, the yield of the specific resin, ease of synthesis, costs related to raw materials and reaction conditions, and the like.
- R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
- the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
- At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups.
- the polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group.
- the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done.
- a group having an ethylenically unsaturated bond is preferred.
- Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), and a (meth)acrylamide group.
- a (meth)acryloyloxy group a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
- R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
- * represents a binding site with another structure.
- R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
- R 201 examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
- alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2
- a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
- the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
- the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
- the number of carbon atoms in the alkylene group is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
- the said alkylene group may have a substituent.
- Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
- the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
- a group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable.
- the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
- the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good.
- tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
- R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
- the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
- acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
- At least one of R 113 and R 114 contains a structure exhibiting the aforementioned base-generating property.
- at least one of R 113 and R 114 preferably has a structure represented by the above formula (1-1) or a structure represented by the above formula (1-2).
- R 113 and R 114 containing a structure exhibiting base-generating property for all of R 113 and R 114 in the specific resin is preferably 0.1 to 100 mol %, more preferably 0.5 to 50 mol %, even more preferably 1 to 20 mol %.
- the polyimide precursor preferably has a fluorine atom in its structure.
- the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.
- the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- an aliphatic group having a siloxane structure there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
- the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
- a 1 and A 2 represent an oxygen atom
- R 111 and R 112 each independently represent a divalent organic group
- R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group
- at least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.
- a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same.
- R 112 has the same definition as R 112 in Formula (5), and the preferred range is also the same.
- the polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
- the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
- the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
- the upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
- the polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
- the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
- the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are within the ranges described above.
- polybenzoxazole precursor Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
- the specific resin when the specific resin contains a repeating unit represented by formula (3), the specific resin preferably contains a structure exhibiting the property of generating a base within the repeating unit represented by formula (3). ) contains the structure represented by the above formula (1-1).
- at least one structure selected from the group consisting of R 121 , R 122 , R 123 and R 124 in formula (3) has the above-mentioned base-generating property (preferably, formula (1-1 ), and a structure ( preferably , It is more preferable to include a structure represented by formula (1-1).
- the specific resin when the specific resin contains a repeating unit represented by formula (3), the specific resin may contain a structure exhibiting the property of generating a base at a location different from the repeating unit represented by formula (3). .
- an aspect including a structure exhibiting a property of generating a base at the end of the specific resin, a structure in which the specific resin is a repeating unit different from the repeating unit represented by formula (3) and exhibits a property of generating a base
- Examples further include a repeating unit containing the above.
- R 123 and R 124 each have the same meaning as R 113 in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
- R 121 represents a divalent organic group.
- the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferred.
- the aliphatic group a linear aliphatic group is preferred.
- R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
- a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
- the dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred.
- the number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, and 4 to 15 is more preferred, and 5-10 is particularly preferred.
- the linear aliphatic group is preferably an alkylene group.
- Dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedi
- Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.
- the dicarboxylic acid containing an aromatic group the following dicarboxylic acid having an aromatic group is preferable, and the following dicarboxylic acid consisting of only a group having an aromatic group and two -COOH is more preferable.
- A is -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 -, and -C(CH 3 ) 2 - represents a divalent group selected from the group consisting of * independently represents a binding site to another structure.
- dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
- R 122 represents a tetravalent organic group.
- the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same.
- R 122 is also preferably a group derived from a bisaminophenol derivative.
- bisaminophenol derivatives having the following aromatic groups are preferred.
- X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-, and * and # respectively represent other structures and represents the binding site of R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.
- R 122 is also preferably a structure represented by the above formula.
- any two of the total four * and # are binding sites with the nitrogen atom to which R 122 in formula (3) binds, and Another two are preferably bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and two * are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded. and two #s are binding sites to the nitrogen atom to which R 122 in formula (3) binds, or two * are binding sites to the nitrogen atom to which R 122 in formula (3) binds and two #s are more preferably binding sites to the oxygen atom to which R 122 in formula (3) binds, and two * are the oxygen to which R 122 in formula (3) binds. More preferably, it is a bonding site with an atom and two #s are bonding sites with a nitrogen atom to which R 122 in formula (3) is bonded.
- the bisaminophenol derivative is also preferably a compound represented by formula (As).
- R 1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc).
- R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
- R3 is a hydrogen atom , a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
- R 1 is alkylene or substituted alkylene.
- alkylene and substituted alkylene for R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which —CH 2 — and —CH(CH 3 ) -, -C(CH 3 ) 2 - have sufficient solubility in solvents while maintaining the effect of high i-line transparency and high cyclization rate when cured at low temperature. It is more preferable in that a polybenzoxazole precursor having excellent properties can be obtained.
- the polybenzoxazole precursor may also contain other types of repeating units in addition to the repeating units of formula (3) above.
- the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that warping due to ring closure can be suppressed.
- Z has an a structure and a b structure
- R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
- At least one of R 3s , R 4s , R 5s and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
- Polymerization of a structure and b structure may be block polymerization or random polymerization.
- the mol % of the Z portion is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and 100 mol % for a+b.
- preferred Z include those in which R 5s and R 6s in the b structure are phenyl groups.
- the molecular weight of the structure represented by formula (SL) is preferably 400-4,000, more preferably 500-3,000.
- tetracarboxylic acid residues include those of R 115 in formula (2).
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, 000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
- the molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
- the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.
- the resin composition contains a plurality of types of polybenzoxazole precursors as specific resins
- the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polybenzoxazole precursor are within the above ranges. preferable. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polybenzoxazole precursors as one resin are within the ranges described above.
- the polyamideimide precursor preferably contains a repeating unit represented by the following formula (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 a monovalent represents an organic group.
- the specific resin when the specific resin contains a repeating unit represented by formula (PAI-2), the specific resin preferably contains a structure exhibiting the property of generating a base within the repeating unit represented by formula (PAI-2). , more preferably contains the structure represented by the above formula (1-1) in the repeating unit represented by the formula (PAI-2).
- a structure preferably , formula ( 1-1 )
- a structure preferably, a structure represented by formula (1-1)
- the specific resin contains a repeating unit represented by formula (PAI-2)
- the specific resin has a structure that exhibits the property of generating a base at a location different from the repeating unit represented by formula (PAI-2).
- an aspect including a structure exhibiting a base-generating property at the end of a specific resin, a repeating unit different from the repeating unit represented by the formula (PAI-2) in the specific resin, and having a base-generating property
- Examples include an aspect further comprising a repeating unit containing the structure shown.
- R 117 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
- the above linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
- alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
- 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 includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
- preferred halogenated alkylene groups include (ditrifluoromethyl)methylene groups and the like.
- the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
- 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 called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be anhydrided.
- the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one of these tricarboxylic acid compounds may be used, or two or more thereof 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 Tricarboxylic acid compounds containing 6 to 20 aromatic groups or groups in which two or more of these are combined via a single bond or a linking group are preferred, and aromatic groups having 6 to 20 carbon atoms or carbon atoms via a single bond or linking group are preferred. More preferred are tricarboxylic acid compounds containing groups in which two or more aromatic groups of numbers 6 to 20 are combined.
- tricarboxylic acid compounds 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 anhydride) and benzoic acid are a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group
- Linked compounds and the like are included.
- These compounds may be compounds in which two carboxy groups are anhydrided (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride). There may be.
- R 111 , A 2 and R 113 have the same meanings as R 111 , A 2 and R 113 in formula (2) above, and preferred embodiments are also the same.
- Polyamideimide precursors may further comprise other repeating units.
- Other repeating units include repeating units represented by the above formula (2) and repeating units 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 a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two The above linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
- alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
- 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 includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
- preferred halogenated alkylene groups include (ditrifluoromethyl)methylene groups and the like.
- the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
- 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.
- linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids examples include acid dihalide compounds.
- One of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used, or two or more thereof may be used.
- the dicarboxylic acid compound or 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 aliphatic group having 3 to 20 carbon atoms.
- a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms.
- dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2- dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid,
- R 111 has the same definition as R 111 in formula (2) above, and preferred embodiments are also the same.
- the polyamideimide precursor preferably has a fluorine atom in its structure.
- the content of fluorine atoms in the polyamideimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine component bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used.
- a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) An aspect in which the total content of units is 50 mol % or more of all repeating units is exemplified.
- the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
- the upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), represented by formula (PAI-1). It may be either a repeating unit or a repeating unit represented by formula (2).
- the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is An embodiment in which it is 50 mol % or more of all repeating units is mentioned.
- the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
- the upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), or represented by formula (PAI-1) may be any of the repeating units provided.
- the weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. .
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.
- the polyamidoimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
- the upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
- the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyamideimide precursors as one resin are within the ranges described above.
- Polyimide precursors and the like for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine.
- a more preferable method is to obtain a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenate the remaining dicarboxylic acid using a halogenating agent, and react it with a diamine.
- the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
- alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
- halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
- organic solvent One type of organic solvent may be used, or two or more types may be used.
- the organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone and the like. are exemplified.
- a basic compound In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction.
- One type of basic compound may be used, or two or more types may be used.
- the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
- terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties.
- Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
- Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
- Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amin
- Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and carboxylic acid anhydrides and carboxylic acid chlorides are more preferred. preferable.
- Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. are mentioned.
- Preferred carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
- a structure exhibiting a base-generating property can be introduced at the end of the specific resin.
- a terminal blocker include a structure exhibiting a base-generating property, a hydroxy group, a thiol group, an amino group, a carboxy group, a carboxylic anhydride region, a carboxylic acid halide group, a sulfonic anhydride group, , a sulfonic acid halide group, or a compound having a reactive group such as a sulfonic acid carboxylic acid anhydride group can be used.
- the terminal blocking agent for example, a compound having a structure exhibiting the property of generating one or more bases and one of the reactive groups described above can be used. Preferred embodiments of the structure exhibiting the property of generating a base are as described above.
- a step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as re-dissolving, re-precipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
- Specific examples of the specific resin are not particularly limited, but preferred are the specific resins used in Examples described later.
- the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. is more preferable, and 50% by mass or more is even more preferable. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass, based on the total solid content of the resin composition. % or less, more preferably 97 mass % or less, and even more preferably 95 mass % or less.
- the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- the resin composition of the present invention preferably contains at least two resins.
- the resin composition of the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
- the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a precursor.
- the resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also simply referred to as "other resins").
- Other resins include polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, polyamideimide precursors, polyamideimides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth) Examples include acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, and the like.
- polyimide precursor polybenzoxazole precursor, and polyamideimide precursor
- resins similar to the specific resins described above can be used, except that they do not have a structure exhibiting the property of generating a base.
- the above-mentioned specific resin is ring-closed, or the same resin as the above-mentioned specific resin except that it does not have a structure that exhibits the property of generating a base. can be used. In that case, the structure may be partially changed in consideration of the solubility in the solvent.
- a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
- a high polymerizable group value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group in 1 g of the resin is 1 ⁇ 10 ⁇ 3 mol/g or more
- the coating properties of the resin composition and the solvent resistance of the pattern (cured product) can be improved. can.
- the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the resin composition. More preferably, it is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred.
- the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, based on the total solid content of the resin composition. It is more preferably 60% by mass or less, even more preferably 50% by mass or less.
- the content of other resins may be low.
- the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less relative to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable.
- the lower limit of the content is not particularly limited as long as it is 0% by mass or more.
- the resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
- the resin composition of the present invention may contain an organometallic complex from the viewpoint of chemical resistance.
- the organometallic complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, and is preferably a compound in which an organic group is coordinated to a metal atom. More preferably, it is a metallocene compound.
- the metallocene compound refers to an organometallic complex having two optionally substituted cyclopentadienyl anion derivatives as ⁇ 5-ligands.
- the organic group is not particularly limited, a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom is preferable.
- Preferred heteroatoms are oxygen, sulfur and nitrogen atoms.
- at least one of the organic groups is preferably a cyclic group, more preferably at least two are cyclic groups.
- the cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, more preferably a 5-membered cyclic group.
- the cyclic group may be a hydrocarbon ring or a heterocyclic ring, but is preferably a hydrocarbon ring.
- a cyclopentadienyl group is preferred.
- the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.
- the metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, and at least one metal selected from the group consisting of titanium, zirconium and hafnium. More preferably, it is at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.
- the organometallic complex may contain two or more metal atoms or may contain only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one kind of metal atom, or may contain two or more kinds of metal atoms.
- the organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, and even more preferably a titanocene compound or a zirconocene compound.
- titanocene compounds are particularly preferred.
- an embodiment in which the organometallic complex has photoradical polymerization initiation ability is also one of preferred embodiments of the present invention.
- having the ability to initiate photoradical polymerization means being able to generate free radicals capable of initiating radical polymerization by irradiation with light.
- a composition containing a radical cross-linking agent and an organometallic complex is irradiated with light in a wavelength range in which the organometallic complex absorbs light and the radical cross-linking agent does not absorb light, radicals
- the presence or absence of photoradical polymerization initiation ability can be confirmed.
- the organometallic complex has photoradical polymerization initiation ability
- the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, and a titanocene compound or a zirconocene compound. is more preferred, and a titanocene compound is particularly preferred.
- the organometallic complex is at least one selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds and hafnocene compounds. More preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds, and at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds More preferred are compounds of the species, and particularly preferred are titanocene compounds.
- the molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.
- Preferred examples of the organometallic complex include compounds represented by the following formula (P).
- M is a metal atom
- each R is independently a substituent.
- the Rs are each independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.
- the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, still more preferably a titanium atom or a zirconium atom, and titanium Atoms are particularly preferred.
- the aromatic group for R in formula (P) includes an aromatic group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, a phenyl group, a 1-naphthyl group, or , 2-naphthyl group and the like.
- the alkyl group for R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an octyl group, and an isopropyl group. , t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
- Halogen atoms for R include F, Cl, Br and I.
- the alkyl group constituting the alkylsulfonyloxy group in R above is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, a methyl group, an ethyl group, a propyl group, an octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
- the above R may further have a substituent.
- substituents include halogen atoms (F, Cl, Br, I), hydroxy groups, carboxy groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxy carbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group and the like.
- organometallic complex examples include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetoacetate)titanium, and diisopropoxybis(acetylacetoacetate).
- nath)titanium bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium tri
- methoxide bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.
- the content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the resin composition of the present invention.
- the lower limit is more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more.
- the upper limit is more preferably 25% by mass or less. 1 type(s) or 2 or more types can be used for an organometallic complex. When two or more are used, the total amount is preferably within the above range.
- the resin composition of the present invention preferably contains a polymerizable compound.
- Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
- the resin composition of the present invention preferably contains a radical cross-linking agent.
- a radical cross-linking agent is a compound having a radically polymerizable group.
- the radically polymerizable group a group containing an ethylenically unsaturated bond is preferred.
- Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
- the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
- the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more.
- the radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
- the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6.
- the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
- the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
- the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
- radical cross-linking agent examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
- addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional is also preferably used.
- addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups
- substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols.
- paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
- the radical cross-linking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
- examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, etc.
- polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.
- JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resins.
- JP-B-46-043946 JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493.
- vinyl phosphonic acid compounds and the like can also be mentioned.
- Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used.
- the journal of the Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.
- dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku ( Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and their (meth)acryloyl groups are ethylene glycol,
- radical cross-linking agents examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd.
- DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation), etc. mentioned.
- radical cross-linking agents examples include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable.
- 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. can also
- the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
- a radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable.
- the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound.
- Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
- the acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
- the resin composition preferably uses a bifunctional methacrylate or acrylate.
- Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate.
- PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
- a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product).
- Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
- N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam
- allyl glycidyl ether are preferably used.
- the monofunctional radical cross-linking agent a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
- Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
- a radical cross-linking agent When a radical cross-linking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
- a single radical cross-linking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
- the resin composition of the present invention also preferably contains other cross-linking agents different from the radical cross-linking agents described above.
- the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them. It is preferable that the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds or reaction products thereof in the composition. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
- the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
- compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups are preferred, and the compounds are preferably selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups. More preferred is a compound having a structure in which at least one group is directly bonded to a nitrogen atom.
- cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methylol group, or A compound having a structure substituted with an alkoxymethyl group can be mentioned.
- the method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
- a melamine-based crosslinking agent is a melamine-based crosslinking agent
- a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent
- an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent.
- a cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
- the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of agents.
- an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine.
- the alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
- the total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
- the molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
- R 100 represents an alkyl group or an acyl group.
- R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
- Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted by an aromatic group include compounds represented by the following general formula.
- X represents a single bond or a divalent organic group
- each R 104 independently represents an alkyl group or an acyl group
- R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is each independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
- R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
- R 5 in the group represented by —C(R 4 ) 2 COOR 5 a group that is decomposed by the action of an acid to generate an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
- R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
- R 36 and R 37 may combine with each other to form a ring.
- alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
- the above alkyl group may be linear or branched.
- a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
- the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
- the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
- an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
- the above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
- the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
- R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- the group that is decomposed by the action of an acid to form an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferred are tertiary alkyl ester groups and acetal groups.
- compounds having an alkoxymethyl group include the following structures.
- Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group.
- Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
- the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available one or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
- melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
- urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol.
- Uril trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril , dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril glycoluril-based crosslinkers such as uril; urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea and bisbutoxymethylurea; monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated
- benzoguanamine cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
- tetramethoxymethylated benzoguanamine monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.
- the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
- Compounds to which a seed group is directly attached are also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate.
- suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
- DML-34X DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.), Nikalac (registered
- the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another cross-linking agent.
- Epoxy compound (compound having an epoxy group) -
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
- the epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warpage of the resin composition of the present invention.
- the epoxy compound preferably contains a polyethylene oxide group.
- the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.
- epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether.
- alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins
- polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether
- epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like.
- Epiclon (registered trademark) 850-S Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-20E, Jamaicaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark)
- n is an integer of 1-5 and m is an integer of 1-20.
- n 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.
- oxetane compounds 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, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned.
- Aron oxetane series manufactured by Toagosei Co., Ltd. eg, OXT-121, OXT-221
- OXT-121, OXT-221 can be suitably used, and these can be used alone or in combination of two or more. good.
- a benzoxazine compound (compound having a benzoxazolyl group)-
- a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.
- benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (the above are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. These may be used alone or in combination of two or more.
- the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 5 to 15% by mass, particularly preferably 1.0 to 10% by mass.
- Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.
- the resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it preferably contains a photopolymerization initiator.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
- the radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). is preferred.
- the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
- any known compound can be used as the photoradical polymerization initiator.
- halogenated hydrocarbon derivatives e.g., 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, etc.
- ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein.
- Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.
- ⁇ -hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
- ⁇ -Aminoketone-based initiators include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
- the compound described in JP-A-2009-191179 whose maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used, the content of which is incorporated herein.
- Acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.
- metallocene compounds examples include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).
- the photoradical polymerization initiator is more preferably an oxime compound.
- an oxime compound By using an oxime compound, the exposure latitude can be improved more effectively.
- Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
- oxime compound examples include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc.
- an oxime compound an oxime-based radical photopolymerization initiator
- DFI-091 manufactured by Daito Chemix Co., Ltd.
- SpeedCure PDO manufactured by SARTOMER ARKEMA
- an oxime compound having the following structure can be used.
- An oxime compound having a fluorene ring can also be used as the photoradical polymerization initiator.
- Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.
- 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. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.
- An oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein.
- the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).
- An oxime compound having a benzofuran skeleton can also be used as the photoradical polymerization initiator.
- Specific examples include OE-01 to OE-75 described in WO 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
- photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.
- an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
- the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
- a benzoyl group may have a substituent.
- substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group.
- a sulfanyl group or an amino group is more preferred.
- the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
- R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
- R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
- R X12 is an electron-withdrawing group
- R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
- oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
- oxime compounds having a specific substituent group shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.
- photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.
- More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds.
- At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .
- the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc.
- benzophenone N,N'-tetraalkyl-4,4'-diaminobenzophenone
- 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthr
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkylbenzoin
- benzyl derivatives such as benzyl dimethyl ketal
- a compound represented by the following formula (I) can also be used.
- R 100 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, Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a carbon number interrupted by one or more oxygen atoms a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R I01 is a group represented by formula (II); R 102 to R 104 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an
- R 105 to R 107 are the same as R 102 to R 104 in formula (I) above.
- radical photopolymerization initiator a difunctional or trifunctional or higher radical photopolymerization initiator may be used.
- a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
- Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
- a photopolymerization initiator When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass, and still 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 photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
- the resin composition may contain a sensitizer.
- a sensitizer absorbs specific actinic radiation and enters an electronically excited state.
- the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, and the like.
- the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and decompose to generate radicals, acids or bases.
- Sensitizers that can be used include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, and indigo compounds.
- sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal).
- the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. more preferably 0.5 to 10% by mass.
- the sensitizers may be used singly or in combination of two or more.
- the resin composition of the present invention may contain a chain transfer agent.
- the chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684.
- Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer )
- Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
- thiol compounds can be preferably used.
- chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein.
- the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable.
- One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
- the resin composition of the present invention may contain a base generator.
- the base generator is a compound capable of generating a base by physical or chemical action.
- Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
- the resin composition when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator.
- the base generator may be an ionic base generator or a non-ionic base generator.
- bases generated from base generators include secondary amines and tertiary amines. There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides.
- nonionic base generator examples include compounds represented by formula (B1), formula (B2), or formula (B3).
- Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 are not hydrogen atoms at the same time. Also, 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, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.
- Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure.
- the cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed.
- the monocyclic ring is preferably a 5- or 6-membered ring, more preferably a 6-membered ring.
- the monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.
- Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have a substituent as long as the effects of the present invention are exhibited.
- Rb 1 and Rb 2 may combine with each other to form a ring.
- the ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring.
- Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent.
- Rb 3 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms).
- an aryl group preferably
- Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
- the compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.
- Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1).
- Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited.
- Rb 13 is preferably an arylalkyl group.
- Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.
- an alkyl group preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms
- an alkenyl group preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3
- an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10
- Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.
- the compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).
- Rb 11 and Rb 12 have the same definitions as Rb 11 and Rb 12 in formula (B1-1).
- Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
- Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.
- an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms
- an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred
- an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12
- L is a divalent hydrocarbon group having a saturated hydrocarbon group on a connecting chain route connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the connecting chain route is represents a hydrocarbon group of 3 or more.
- R N1 and R N2 each independently represent a monovalent organic group.
- the term “connected chain” refers to the shortest (minimum number of atoms) of atomic chains on a path connecting two atoms or groups of atoms to be connected.
- L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group
- the linking chain is composed of four carbon atoms, and on the route of the linking chain
- the number of atoms of (that is, the number of atoms constituting the linked chain, hereinafter also referred to as "linked chain length" or "linked chain length”) is 4.
- the number of carbon atoms in L (including carbon atoms other than carbon atoms in the connecting chain) in formula (B3) is preferably 3-24.
- the upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more.
- the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred.
- the linking chain length of L is preferably 4 or 5, most preferably 4.
- Specific preferred compounds of the base generator include, for example, compounds described in paragraph numbers 0102 to 0168 of WO2020/066416, and compounds described in paragraph numbers 0143 to 0177 of WO2018/038002. mentioned.
- the base generator preferably contains a compound represented by the following formula (N1).
- R N1 and R N2 each independently represent a monovalent organic group
- R C1 represents a hydrogen atom or a protecting group
- L represents a divalent linking group
- L is a divalent linking group, preferably a divalent organic group.
- the linking chain length of the linking group is preferably 1 or more, more preferably 2 or more.
- the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
- the linking chain length is the number of atoms present in the atomic arrangement that provides the shortest path between two carbonyl groups in the formula.
- R 1 N1 and R 2 N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and a hydrocarbon group ( preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 10 is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and an aliphatic hydrocarbon groups are preferred.
- a monovalent organic group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms
- a hydrocarbon group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms
- an aliphatic hydrocarbon group
- an aliphatic hydrocarbon group as R N1 and R N2 because the generated base has high basicity.
- the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are in the aliphatic hydrocarbon chain or in the aromatic ring, You may have an oxygen atom in the substituent.
- an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
- Aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains.
- Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms.
- Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
- Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
- Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
- Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
- the alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
- An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
- R 3 N1 and R 3 N2 are preferably alkyl groups having 5 to 12 carbon atoms, from the viewpoint of raising the boiling point of the decomposition base described below.
- a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
- RN1 and RN2 may be linked to each other to form a ring structure.
- the chain may have an oxygen atom or the like.
- the cyclic structure formed by R N1 and R N2 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
- the cyclic structure to be formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like can be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring are preferably mentioned.
- N1 nitrogen atom in formula (N1)
- R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
- the protective group is preferably a protective group that is decomposed by the action of an acid or a base, and preferably includes a protective group that is decomposed by an acid.
- protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain.
- Chain or cyclic alkyl groups include methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group and the like.
- the chain alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, and the like. mentioned.
- Cyclic alkyl groups having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, tetrahydropyranyl (THP) group and the like.
- the divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group.
- the hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred.
- the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
- the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- a group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.
- linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
- a linear or branched alkenylene group, a cyclic alkenylene group, an arylene group and an arylenealkylene group are preferred.
- the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
- the cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
- the group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
- An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
- the alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- the linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms.
- the cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
- the number of C ⁇ C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
- the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
- a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.
- base generators include the following, but the present invention should not be construed as being limited thereto.
- the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
- the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
- Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
- ammonium salts include the following compounds, but the present invention is not limited thereto.
- iminium salts include the following compounds, but the present invention is not limited thereto.
- the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
- the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
- the upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
- One or two or more base generators can be used. When two or more are used, the total amount is preferably within the above range.
- the resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent.
- the solvent is preferably an organic solvent.
- Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
- Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
- 3-alkyloxypropionic acid alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- 2-alkyloxypropionate alkyl esters e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
- 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
- ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, 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, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Preferred examples include monobutyl ether acetate
- Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like.
- Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
- Suitable sulfoxides include, for example, dimethyl sulfoxide.
- Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
- Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.
- a combination of dimethyl sulfoxide and ⁇ -butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly
- the content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 20 to 70% by mass.
- the solvent content may be adjusted according to the desired thickness of the coating and the method of application.
- the resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.
- the resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like.
- metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and ⁇ -ketoesters. compounds, amino compounds, and the like.
- silane coupling agent examples include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992.
- Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein.
- silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
- xypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimeth
- Aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
- the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved.
- One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
- the resin composition of the present invention preferably further contains a migration inhibitor.
- a migration inhibitor By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
- Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds.
- heterocyclic rings pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring,
- triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
- an ion trapping agent that traps anions such as halogen ions can be used.
- Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656.
- the compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compound described in paragraph 0166 of WO 2015/199219, etc. can be used, and these The contents are incorporated herein.
- migration inhibitors include the following compounds.
- the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.
- migration inhibitor Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.
- the resin composition of the present invention preferably contains a polymerization inhibitor.
- Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
- Specific compounds of polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl hydroxylamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol,
- the content of the polymerization inhibitor is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
- polymerization inhibitor Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
- the resin composition of the present invention may optionally contain various additives such as photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization agents, and the like, which are known in the art, as long as the effects of the present invention can be obtained.
- additives such as photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization agents, and the like, which are known in the art, as long as the effects of the present invention can be obtained.
- Initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-coagulants, phenolic compounds, other polymer compounds, plasticizers and other auxiliary agents (e.g. defoamer, flame retardant, etc.) ) and the like can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No.
- the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
- surfactant various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used.
- the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
- the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved.
- a surfactant in the resin composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved.
- the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved.
- the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
- fluorine-based surfactants include Megaface F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florard FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above , Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.
- Fluorine-based surfactants compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, and these contents are incorporated herein.
- a block polymer can also be used as a fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated herein.
- the fluorosurfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (meta).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
- the weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
- a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein.
- Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
- the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
- a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.
- silicone-based surfactants examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Dow Corning Co., Ltd. ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd. ), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie Co., Ltd.).
- Hydrocarbon surfactants include, for example, Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (manufactured by Takemoto Oil & Fat Co., Ltd.), and the like.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Examples include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
- cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.
- anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).
- the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
- the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after coating. may be unevenly distributed on the surface of the
- the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
- the resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator.
- a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved.
- the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
- thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
- thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass.
- One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
- the resin composition of the present invention may contain inorganic particles.
- inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.
- the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, still more preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferred.
- the average particle size of the inorganic particles is the primary particle size and the volume average particle size.
- the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.
- the composition of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
- salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like.
- benzophenone-based UV absorbers examples include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- and hydroxy-4-octoxybenzophenone.
- benzotriazole-based UV absorbers examples include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 '-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5' -(1,
- Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
- examples of triazine-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl )-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -mono(hydroxyphenyl)triazine compounds such as 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(
- the above various ultraviolet absorbers may be used singly or in combination of two or more.
- the composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.
- the resin composition of this embodiment may contain an organic titanium compound. By including the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
- Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained.
- titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate) , titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
- Tetraalkoxytitanium compounds for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide.
- titanium tetramethoxypropoxide titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl) butoxide ⁇ ] and the like.
- Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
- Monoalkoxy titanium compounds for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide and the like.
- Titanium oxide compounds for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
- the organotitanium compound at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance.
- titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.
- the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
- the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
- compositions of the present invention may contain antioxidants.
- an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials.
- Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound.
- Preferred phenolic compounds include hindered phenolic compounds.
- a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent.
- the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
- Phosphorus-based antioxidants can also be suitably used as antioxidants.
- a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
- antioxidants examples include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
- compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein.
- the composition of the present invention may also contain latent antioxidants, if desired.
- the latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
- a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
- latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein.
- Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
- Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
- R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). represents a group.
- R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom.
- k represents an integer of 1 to 4;
- the compound represented by formula (3) suppresses oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin. In addition, metal oxidation can be suppressed by the antirust action on the metal material.
- R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, - O--, --NH--, --NHNH--, combinations thereof, and the like, which may further have a substituent.
- Examples of compounds represented by general formula (3) include the following, but are not limited to the structures below.
- the amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment. The interaction with the agent improves the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present embodiment may contain an anti-aggregation agent as necessary.
- Anti-aggregating agents include sodium polyacrylate and the like.
- the aggregation inhibitor may be used alone or in combination of two or more.
- the composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.
- the resin composition of the present embodiment may contain a phenolic compound as necessary.
- phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
- one type of phenolic compound may be used alone, or two or more types may be used in combination.
- the composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.
- Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof.
- Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
- composition of the present invention may or may not contain other polymer compounds, but when it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
- the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity.
- the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.
- the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
- metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.
- a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention.
- the raw material constituting the product is filtered through a filter, or the inside of the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.
- the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred.
- those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
- Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
- ion exchange treatment and the like are preferably mentioned.
- a conventionally known container can be used as the container for the resin composition of the present invention.
- the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
- a cured product of this resin composition By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
- the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. Curing of the resin composition is preferably by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and 170°C. It is particularly preferred to be in the range of -350°C.
- the form of the cured product of the resin composition is not particularly limited, and can be selected from film-like, rod-like, spherical, pellet-like, etc. according to the application.
- this cured product is preferably in the form of a film.
- pattern processing of the resin composition can be used to form protective films on walls, form via holes for conduction, adjust impedance, capacitance or internal stress, and impart heat dissipation functions. You can also choose the shape.
- the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
- the shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
- the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. If it is 70% or more, a cured product having excellent mechanical properties may be obtained.
- the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
- the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
- the resin composition of the present invention can be prepared by mixing the components described above.
- the mixing method is not particularly limited, and conventionally known methods can be used. Mixing can be performed by mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like.
- the temperature during mixing is preferably 10-30°C, more preferably 15-25°C.
- the filter pore size is, for example, 5 ⁇ m or less, 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. HDPE (high density polyethylene) is more preferable when the material of the filter is polyethylene.
- a filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use.
- filters with different pore sizes or materials may be used in combination.
- a connection mode for example, a mode in which an HDPE filter with a pore size of 1 ⁇ m is connected in series as a first stage and an HDPE filter with a pore size of 0.2 ⁇ m as a second stage are connected in series.
- various materials may be filtered multiple times.
- circulation filtration may be used.
- you may filter by pressurizing.
- the pressure to be applied is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less.
- impurities may be removed using an adsorbent.
- You may combine filter filtration and the impurity removal process using an adsorbent.
- a known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the resin composition filled in the bottle may be subjected to a degassing step under reduced pressure.
- the method for producing a cured product of the present invention includes a film forming step of applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film, a step of selectively exposing the film, and a step of exposing the film. and a heating step of heating the pattern at a temperature of 50° C. or higher and 250° C. or lower, wherein the precursor of the cyclized resin is a base in the heating step.
- the above-mentioned specific resin contained in the resin composition of the present invention is preferably exemplified.
- the resin composition used in the film forming step of the method for producing a cured product of the present invention is the resin composition of the present invention described above.
- the resin composition of the present invention can be used in a film-forming step in which a film is formed by applying it onto a substrate.
- the method for producing a cured product of the present invention includes a film forming step of applying the resin composition onto a substrate to form a film.
- the type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.) ), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc., and are not particularly limited.
- semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.
- a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate and a mold substrate are more preferable.
- these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
- HMDS hexamethyldisilazane
- the shape of the substrate is not particularly limited, and may be circular or rectangular.
- the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm.
- the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
- the base material for example, a plate-like base material (substrate), preferably a panel-like base material (substrate) is used.
- the resin layer or metal layer serves as the base material.
- Specific means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, An inkjet method and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred.
- a film having a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition according to the method.
- the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc.
- slit coating and spray coating are preferable for rectangular substrates.
- method, inkjet method, and the like are preferred.
- the spin coating method for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
- a method of transferring a coating film, which is formed on a temporary support in advance by the application method described above, onto a base material can be applied.
- the transfer method the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be preferably used in the present invention.
- a step of removing excess film at the edge of the substrate may be performed.
- processes include edge bead rinsing (EBR), back rinsing, and the like.
- EBR edge bead rinsing
- a pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
- the film may be subjected to a step of drying the formed film (layer) to remove the solvent (drying step) after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Moreover, the drying step is preferably performed after the film formation step and before the exposure step.
- the drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction.
- the drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
- the ratio of the base generating group concentration X in the upper 50% of the thickness direction of the film to the base generating group concentration Y in the lower 50% of the film formed in the film forming step X/Y is preferably 0.90 ⁇ X/Y ⁇ 1.10. According to such an aspect, it is presumed that the base is likely to be generated in a nearly uniform state within the film, and that a cured product pattern having excellent rectangularity, for example, can be obtained.
- the base-generating group includes both a structure that exhibits the property of generating a base contained in the specific resin and a structure that exhibits the property of generating a base contained in the above-mentioned base generator.
- the X/Y is preferably 0.92 ⁇ X/Y ⁇ 1.08, more preferably 0.94 ⁇ X/Y ⁇ 1.06. .
- the above X/Y can be measured by the method described in Examples below.
- the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed in the film forming step.
- Selectively exposing means exposing a portion of the film.
- the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions).
- the amount of exposure is not particularly defined as long as the resin composition of the present invention can be cured . is more preferred.
- the exposure wavelength can be appropriately determined in the range of 190-1,000 nm, preferably 240-550 nm.
- the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser ( wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
- semiconductor laser wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355
- the resin composition of the present invention exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
- the method of exposure is not particularly limited as long as at least a part of the film made of the resin composition of the present invention is exposed. Exposure using a photomask, exposure by a laser direct imaging method, etc. mentioned.
- the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the exposed film in the exposure step.
- the post-exposure heating step can be performed after the exposure step and before the development step.
- the heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
- the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
- the heating rate in the post-exposure heating step is preferably from 1 to 12° C./min, more preferably from 2 to 10° C./min, still more preferably from 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature. Also, the rate of temperature increase may be appropriately changed during heating.
- the heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used. It is also preferable to perform the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
- the method for producing a cured product of the present invention includes a development step of developing a film exposed in the exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
- development in which the unexposed portion of the film is removed by the development process is called negative development
- development in which the exposed portion of the film is removed by the development process is called positive development.
- Examples of the developer used in the development step include a developer containing an alkaline aqueous solution or an organic solvent.
- basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
- TMAH tetramethylammonium hydroxide
- potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide , butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)am
- the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.
- the organic solvent may be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
- 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxy methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
- 2-alkyloxypropionate alkyl esters e.g.
- methyl 2-alkyloxypropionate, 2- ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid ethyl
- methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g.
- ethers such as 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol monoethyl ether acetate
- the organic solvent can be used singly or in combination of two or more.
- a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, and cyclopentanone and ⁇ -butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.
- the content of the organic solvent relative to the total weight of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass.
- the developer may further contain other components.
- Other components include, for example, known surfactants and known antifoaming agents.
- the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and a method of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle.
- the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned. From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable.
- the method of supplying with a spray nozzle is more preferable.
- the substrate is spun to remove the developer from the substrate.
- a step of removing from above may be employed, and this step may be repeated multiple times.
- the method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material.
- a process of vibrating with sound waves or the like and a process of combining them can be employed.
- the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
- the pattern may be washed (rinsed) with a rinse.
- a method of supplying the rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
- Rinse liquid When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse.
- a solvent different from the solvent contained in the developer for example, water, an organic solvent different from the organic solvent contained in the developer
- the rinse liquid is used as the rinse liquid. be able to.
- the organic solvent includes esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
- 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3- methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
- 2-alkyloxypropionate alkyl esters e.g.
- methyl 2-alkyloxypropionate 2 -ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate ethyl acid)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g.
- ethers such as 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether a
- the organic solvent can be used singly or in combination of two or more.
- the organic solvent can be used singly or in combination of two or more.
- cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are more preferred. More preferred.
- the rinse liquid contains an organic solvent
- the rinse liquid is preferably 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and 90% by mass or more of the organic solvent. is more preferred. Further, 100% by mass of the rinse liquid may be an organic solvent.
- the rinse solution may further contain other components.
- Other components include, for example, known surfactants and known antifoaming agents.
- the method of supplying the rinse solution is not particularly limited as long as the desired pattern can be formed.
- a method of continuously supplying the rinsing liquid onto the material using means such as a straight nozzle.
- there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc. there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable.
- the method of supplying the rinsing liquid with a spray nozzle is more preferable.
- the rinsing step is preferably a step of supplying the rinse liquid to the film after exposure through a straight nozzle or a step of continuously supplying the same, and more preferably a step of supplying the rinse liquid through a spray nozzle.
- the method of supplying the rinse liquid in the rinse step includes a process in which the rinse liquid is continuously supplied to the base material, a process in which the rinse liquid is kept substantially stationary on the base material, and a process in which the rinse liquid is kept on the base material in a substantially stationary state. A process of vibrating with sound waves or the like and a process of combining them can be adopted.
- the rinse time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.
- the number of moles E of the base generating groups present in the film after the exposure step and before the development step, which remains as the pattern after the development step, and the number of moles E of the base generating group after the development step preferably exceeds 0.9. According to such an embodiment, the reduction of base-generating groups due to development is suppressed, and it is considered that a cured product having excellent elongation at break can be easily obtained.
- the film after the exposure process and before the development process, which remains as the pattern after the development process refers to the portion of the film that remains after development.
- the above-mentioned base-generating group includes both a structure exhibiting the property of generating a base contained in the specific resin and a structure exhibiting the property of generating a base contained in the above-mentioned base generator.
- the structure exhibiting this base-producing property is also included in the base-generating group.
- the F/E is preferably 0.92 or more, more preferably 0.94 or more.
- the upper limit of F/E is not particularly limited, and can be, for example, 5.0 or less.
- a base generator for example, by adding a base generator to at least one of the developer and the rinse solution, or by contacting the pattern with a processing solution containing the base generator after development or after rinsing, it is possible to remove the base generating groups after the development step or the rinse step.
- the content can also be increased.
- the above F/E can be measured by the method described in Examples below.
- the pattern obtained by the developing step (pattern after rinsing if the rinsing step is performed) is subjected to a heating step of heating the pattern obtained by the above developing at a temperature of 50°C or higher and 250°C or lower. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step. Moreover, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the developing step or a film obtained by the film forming step. In the heating step, a resin such as a polyimide precursor is cyclized into a resin such as polyimide.
- the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 250°C, more preferably 150 to 350°C, still more preferably 150 to 250°C, even more preferably 160 to 250°C, particularly 160 to 230°C. preferable.
- the heating temperature can be appropriately set as a temperature at which a base is generated from the specific resin.
- the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base generated from the specific resin or the base generator by heating.
- Heating in the heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
- the rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min.
- By setting the temperature rise rate to 1°C/min or more it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity.
- the residual stress of the object can be relaxed.
- 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 up to the maximum heating temperature is started.
- the temperature of the film (layer) after drying is, for example, the boiling point of the solvent contained in the resin composition of the present invention.
- the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, even more preferably 15 to 240 minutes.
- the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, and further preferably 100° C. or higher, from the viewpoint of adhesion between layers. 120° C. or higher is particularly preferred.
- the upper limit of the heating temperature is preferably 250° C. or lower, more preferably 240° C. or lower, and even more preferably 230° C. or lower.
- Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
- the pretreatment step is preferably performed for 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 first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.
- the heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or under reduced pressure, in order to prevent decomposition of the specific resin.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
- a heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.
- the pattern obtained by the developing step (or the pattern after rinsing when the rinsing step is performed) may be subjected to a post-development exposure step of exposing the pattern after the developing step, in addition to the heating step.
- the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step.
- the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
- the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator is promoted. can do.
- the post-development exposure step at least part of the pattern obtained in the development step may be exposed, but it is preferable to expose the entire pattern.
- the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. preferable.
- the post-development exposure step can be performed using, for example, the light source used in the exposure step described above, and broadband light is preferably used.
- the pattern obtained by the development step may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of the heating step and the post-development exposure step). is preferred.
- the metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.
- the method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, use the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. can do.
- photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used.
- a preferred embodiment of plating is electroplating using a copper sulfate or copper cyanide plating solution.
- the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m, at the thickest part.
- the ratio A / B of the ring closure ratio A on the surface of the obtained cured product opposite to the side in contact with the substrate and the ring closure ratio B on the surface on the side in contact with the substrate is preferably 0.90 ⁇ A/B ⁇ 1.10.
- film shrinkage is approximately the same in the vicinity of the side in contact with the substrate and in the vicinity of the side opposite to the side in contact with the substrate, so it is presumed that the rectangularity of the cured product is improved.
- the ring closure rate means the imidization rate if the specific resin is a polyimide precursor or polyamideimide precursor, and the oxazole conversion rate if it is a polybenzoxazole precursor.
- A/B is preferably 0.92 ⁇ A/B ⁇ 1.08, more preferably 0.94 ⁇ A/B ⁇ 1.06. .
- the above A/B can be measured by the method described in Examples below.
- the ratio C/D between the width shrinkage rate C and the width shrinkage rate D at the lower end is preferably 0.90 ⁇ C/D ⁇ 1.10.
- the C/D is preferably 0.92 ⁇ C/D ⁇ 1.08, more preferably 0.94 ⁇ C/D ⁇ 1.06. .
- the C/D can be measured by the method described in Examples below.
- Fields to which the cured product of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and stress buffer films.
- pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above may be used.
- the method for producing the cured product of the present invention or the cured product of the present invention can also be used for the production of plates such as offset plates or screen plates, for etching molded parts, for protective lacquers and dielectrics in electronics, especially microelectronics. It can also be used for the production of layers and the like.
- the laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
- the laminate of the present invention is a laminate containing two or more layers made of a cured product, and may be a laminate in which three or more layers are laminated. Of the two or more layers of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and the shrinkage of the cured product, or the deformation of the cured product due to the shrinkage, etc. From the viewpoint of suppression, it is also preferable that all the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
- the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.
- the laminate of the present invention includes two or more layers made of the cured product, and a metal layer between any of the layers made of the cured product.
- the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the cured product between the methods for producing the cured product that are performed multiple times. Preferred aspects of the metal layer forming step are as described above.
- the laminate for example, a laminate containing at least a layer structure in which three layers of a layer made of the first cured product, a metal layer, and a layer made of the second cured product are laminated in this order is preferable. be done.
- both the layer comprising the first cured product and the layer comprising the second cured product are layers comprising the cured product of the present invention.
- the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition.
- the metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.
- the method for producing a laminate of the present invention includes a lamination step.
- the lamination step means that the surface of the pattern (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and development It is a series of steps including performing at least one of the post-exposure steps in this order. However, at least one of (a) the film forming step and (d) the heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, (e) a metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.
- a surface activation treatment process may be further performed.
- a plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
- the lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
- a configuration of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferable, and a configuration of 2 to 9 layers is more preferable.
- Each of the layers described above may have the same composition, shape, film thickness, etc., or may differ from each other.
- a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer.
- the film forming step, (b) the exposure step, (c) the developing step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order.
- the film forming step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order.
- the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least part of the metal layer and the resin composition layer to surface activation treatment.
- the surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to surface activation treatment.
- the metal layer forming step may be performed.
- the surface activation treatment may be performed only on at least part of the metal layer, may be performed only on at least part of the resin composition layer after exposure, or may be performed on the metal layer and the resin composition layer after exposure. Both may be done at least partially, respectively.
- the surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which the resin composition layer is formed.
- the surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which the resin composition layer is formed.
- the adhesion to the resin composition layer (film) provided on the surface can be improved.
- it is preferable to perform the surface activation treatment on part or all of the resin composition layer (resin layer) after exposure By subjecting the surface of the resin composition layer to the surface activation treatment in this way, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface that has undergone the surface activation treatment.
- the resin composition layer when the resin composition layer is cured, such as in the case of negative development, it is less likely to be damaged by surface treatment, and the adhesion is likely to be improved.
- Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, and CF 4 /O 2 . , NF 3 /O 2 , SF 6 , NF 3 , NF 3 /O 2 etching treatment, surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then amino groups and thiol groups.
- UV ultraviolet
- the treatment is selected from immersion treatment in an organic surface treatment agent containing at least one compound and mechanical surface roughening treatment using a brush.
- Plasma treatment is preferred, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferred.
- the energy is preferably 500-200,000 J/m 2 , more preferably 1000-100,000 J/m 2 , most preferably 10,000-50,000 J/m 2 .
- the present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention. Moreover, this invention also discloses the manufacturing method of the semiconductor device containing the manufacturing method of the hardened
- Specific examples of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can refer to the descriptions in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. The contents of which are incorporated herein.
- the precursor of the cyclized resin of the present invention comprises a repeating unit represented by the following formula (2), a repeating unit represented by the formula (3), and a repeating unit represented by the formula (PAI-2). It contains at least one repeating unit selected from the group.
- 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
- at least one of R 111 , R 115 , R 113 and R 114 is represented by the following formula (1-1) Including structure.
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. and at least one of R 121 , R 122 , R 123 and R 124 includes a structure represented by the following formula (1-1).
- 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 a monovalent and at least one of R 117 , R 111 and R 113 includes a structure represented by the following formula (1-1).
- each R 1 is independently a hydrogen atom or a monovalent organic group
- two R 1s may be linked to form a ring structure
- L 1 is a trivalent organic represents a group
- * represents a binding site with another structure.
- the precursor of the cyclized resin of the present invention is a group consisting of a repeating unit represented by formula (2), a repeating unit represented by formula (3), and a repeating unit represented by formula (PAI-2).
- the specific resin contained in the resin composition of the present invention described above, except that it contains at least one type of repeating unit selected from and contains the structure represented by the above formula (1-1) in these repeating units is synonymous with, and preferred embodiments are also the same.
- preferred embodiments of formula (1-1) are the same as the preferred embodiments of formula (1-1) in the specific resin described above.
- preferred embodiments of formula (2), formula (3) and formula (PAI-2) include the structure represented by formula (1-1) above in the structure, except that the structure of formula (2 ), the same as the preferred embodiments of formulas (3) and (PAI-2).
- Resin 1 When the molecular weight of Resin 1 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.
- Resin 1 is presumed to contain a repeating unit having a structure represented by formula (P-1) below, where R is a structure represented by formula (R-1).
- R is a structure represented by formula (R-1).
- the description of mol % in formula (R-1) represents the molar ratio of each structure.
- * in the formula represents a bonding site with an oxygen atom to which R bonds.
- reaction mixture was then cooled to -10°C and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10 ⁇ 5°C.
- thionyl chloride was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5° C. over 60 minutes. and the mixture was stirred at room temperature for 2 hours.
- 10.0 g of ethanol (terminal blocking agent) was added and stirred at room temperature for 1 hour.
- the polyimide precursor was then precipitated by adding 6000 g of water, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes.
- a precipitate (polyimide precursor solid) after stirring was collected by filtration and dissolved in 500 g of tetrahydrofuran.
- 6000 g of water (poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes.
- the precipitate (polyimide precursor solid) after stirring was filtered again and dried under reduced pressure at 45° C. for 3 days.
- the ion exchange resin was removed by filtration, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate.
- the precipitate was collected by filtration and dried at 45° C. under reduced pressure for 24 hours to obtain 45.1 g of Resin 2.
- Mw weight average molecular weight
- Resin 2 with Mw of 4,500, Resin 2 with Mw of 7,500, Resin 2 with Mw of 10,000, Mw Resin 2 with Mw of 30,000, Resin 2 with Mw of 50,000, and Resin 2 with Mw of 100,000 were also synthesized.
- Resin 2 is presumed to contain a repeating unit having a structure represented by formula (P-1) below, where R is a structure represented by formula (R-1).
- R is a structure represented by formula (R-1).
- the description of mol % in formula (R-1) represents the molar ratio of each structure.
- * in the formula represents a bonding site with an oxygen atom to which R bonds.
- Resins 24 to 35 are presumed to be resins containing repeating units represented by formulas (P-24) to (P-35), respectively.
- the subscripts in parentheses represent the molar ratio of each repeating unit.
- the description of mol % in each formula represents the molar ratio of each structure.
- Resins 24 to 35 were synthesized using raw materials shown in Table 2 or Table 3 below.
- Comparative Resin 1 was a structure represented by the following formula (CP-1).
- each resin composition was obtained by mixing the components shown in the table below.
- the components shown in the table below were mixed to obtain each comparative composition.
- the content (mixture amount) of each component described in the table was the amount (parts by mass) described in the column of "parts by mass” in each column of the table.
- the resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.8 ⁇ m.
- the description of "-" indicates that the composition does not contain the corresponding component.
- the entire surface of the resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ/cm 2 . exposed.
- the exposure wavelength is described in "Exposure wavelength (nm)" in the table.
- Exposure wavelength (nm) in the examples described as “Positive” in the column of development conditions in the table, exposure was not performed.
- the resin composition layer was immersed in the developer shown in the table to obtain a film (pattern) after development.
- the films before and after development were each subjected to 1 H-NMR measurement and HPLC measurement using heavy DMSO to quantify the base-generating component (molar amount of base-generating group) remaining in the film before and after development.
- the ratio F/E of the molar amount E of the base-generating groups present in the film before development to the molar amount F of the base-generating groups present in the film after development was calculated and described in
- a cured resin composition layer (cured product) was produced by the same method as the evaluation of elongation at break, which will be described later.
- the silicon wafer on which the cured product was formed was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid to separate the cured product from the silicon wafer.
- FT-IR measurement was performed on each of the surface side (the side opposite to the silicon wafer) and the side that was in contact with the silicon wafer of the obtained peeled film to calculate the ring closure ratio of each surface.
- FT-IR measurement was performed as follows.
- the peak intensity P1 near 1377 cm ⁇ 1 which is the absorption peak derived from the imide structure, in the infrared absorption spectrum measured by FT-IR is measured on the surface side and silicon. Each measurement was made on the side that was in contact with the wafer. Next, after heat-treating the cured product at 350° C. for 1 hour, the FT-IR measurement was performed again, and the peak intensity P2 near 1377 cm ⁇ 1 was obtained for each of the surface side and the side in contact with the silicon wafer. . Using the obtained peak intensities P1 and P2, the imidization rate (ring closure rate) of the polyimide was determined according to the following formula.
- Imidation rate (%) (peak intensity P1/peak intensity P2) x 100
- the peak intensity Q1 near 1650 cm ⁇ 1 which is the absorption peak derived from the amide structure, is determined, and then the absorption intensity of the aromatic ring seen near 1490 cm ⁇ 1 is standardized.
- the infrared absorption spectrum is measured again, the peak intensity Q2 near 1650 cm ⁇ 1 is obtained, and the absorption intensity of the aromatic ring seen near 1490 cm ⁇ 1 is normalized. did.
- the oxazolization rate (ring closure rate) of polybenzoxazole was determined according to the following formula.
- Oxazolization rate (%) (standardized value of peak intensity Q1/standardized value of peak intensity Q2) x 100
- the ratio A / B of the ring closure rate A on the surface of the cured product on the side opposite to the side in contact with the silicon wafer and the ring closure rate B on the surface on the side in contact with the silicon wafer is calculated. B” column.
- a cured film having a 1:1 line-and-space pattern with a thickness of 20 ⁇ m and a pitch of 10 ⁇ m was obtained by the same method as the evaluation of pattern rectangularity described later, except that the film thickness was changed and the heating time was changed to 180 minutes. .
- the width shrinkage rate at the upper end and the width shrinkage rate at the lower end of the line pattern were calculated.
- the ratio C/D of the width shrinkage rate C at the upper end of the line pattern and the width shrinkage rate D at the lower end was calculated and described in the column of "C/D" in the table.
- the temperature was raised at a rate of 10° C./min, and after reaching 230° C., the above temperature was maintained for 180 minutes.
- the cured resin composition layer (cured product) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer.
- the peeled cured product was punched out using a punching machine to prepare a test piece having a width of 3 mm and a length of 30 mm.
- the longitudinal elongation of the obtained test piece was measured using a tensile tester (Tensilon) under an environment of a crosshead speed of 300 mm / min, 25 ° C., 65% RH (relative humidity), according to JIS-K6251. Measured according to Each measurement was performed five times, and the arithmetic average value of the elongation rate (elongation at break) when the test piece was broken in the five measurements was used as an index value.
- the evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "elongation at break" column in the table. It can be said that the larger the index value, the more excellent the film strength of the cured product.
- C The index value was 55% or more and less than 60%.
- D The index value was less than 55%.
- each resin composition or comparative composition was applied (applied) in layers on a silicon wafer by spin coating to form a resin composition film.
- the silicon wafer to which the obtained resin composition film was applied was dried on a hot plate at 100° C. for 5 minutes to form a resin composition film on the silicon wafer.
- the resin composition film on the silicon wafer was exposed to light with an exposure energy of 500 mJ/cm 2 using the exposure wavelength described in the "Exposure wavelength ( ⁇ m)" column of the table.
- the exposure was performed through a mask (a binary mask having a pattern of 1:1 line and space and a line width of the line width described in the "pattern size ( ⁇ m)" column in the table).
- a mask a binary mask having a pattern of 1:1 line and space and a line width of the line width described in the "pattern size ( ⁇ m)" column in the table.
- development was performed for 60 seconds using a 2.5% by mass tetramethylammonium hydroxide aqueous solution, followed by rinsing with pure water for 20 seconds. to obtain a line-and-space pattern of the resin composition film after exposure.
- the resin composition film was developed using cyclopentanone for 60 seconds and rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds. of line-and-space patterns are obtained.
- PMEA propylene glycol monomethyl ether acetate
- curing was performed under specified curing (curing) conditions. Specifically, in the example in which a numerical value is described in the column of "curing temperature (°C)", a hot plate is used to heat the resin composition layer after the exposure in a nitrogen atmosphere at 10°C/min. After reaching the temperature indicated in the "Cure temperature (°C)" column of the table, the above temperature was maintained for the time indicated in the "Cure time (min)” column of the table.
- the taper angle between the surface of the silicon wafer (substrate surface) and the side surface of the cured film was measured and evaluated according to the following evaluation criteria.
- the evaluation results are shown in the "Pattern Rectangularity" column of the table. It can be said that the closer the taper angle is to 90°, the better the pattern shape is, as the taper angle does not exceed 90° and the cross-sectional shape of the pattern is not constricted.
- C The taper angle was 75° or more and less than 80°.
- D The taper angle was less than 75°, the cross-sectional shape of the pattern was an inverse tapered shape with a taper angle exceeding 90°, or the cross-sectional shape of the pattern was constricted.
- each resin composition or comparative composition was applied (applied) in layers on a silicon wafer by spin coating to form a resin composition film.
- the silicon wafer to which the obtained resin composition film was applied was dried on a hot plate at 100° C. for 5 minutes to form a resin composition film on the silicon wafer.
- the resin composition film on the silicon wafer was exposed with an exposure energy of 500 mJ/cm 2 using the exposure wavelength described in the "Exposure wavelength (nm)" column of the table.
- the exposure was carried out through a mask (a binary mask with a pattern of 1:1 line and space and a line width of the line width described in the column of "Pattern size ( ⁇ m)" in the table).
- a mask a binary mask with a pattern of 1:1 line and space and a line width of the line width described in the column of "Pattern size ( ⁇ m)" in the table.
- development was performed for 60 seconds using a 2.5% by mass tetramethylammonium hydroxide aqueous solution, followed by rinsing with pure water for 20 seconds. to obtain a line-and-space pattern of the resin composition film after exposure.
- the resin composition film was developed using cyclopentanone for 60 seconds and rinsed with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds.
- PMEA propylene glycol monomethyl ether acetate
- line-and-space patterns are obtained.
- the resulting line-and-space pattern was observed from the top of the pattern with a length-measuring scanning electron microscope (SEM, Hitachi Ltd. S-9380II), and the line width was measured in the range of 2000 ⁇ m along the edges of the line pattern in the longitudinal direction.
- SEM length-measuring scanning electron microscope
- S-9380II scanning electron microscope
- the line width was measured in the range of 2000 ⁇ m along the edges of the line pattern in the longitudinal direction.
- the standard deviation ⁇ was determined for the measurement dispersion of the line width, and 3 ⁇ was calculated. A smaller value indicates better performance.
- the use of the resin composition of the present invention improves the rectangularity of the pattern in the resulting cured product.
- the comparative composition in Comparative Example 1 does not contain the specific resin. It can be seen that in such an embodiment, the rectangularity of the pattern in the resulting cured product is poor.
- Example 101 The resin composition used in Example 1 was applied in a layer by spin coating to the surface of the thin copper layer of the resin substrate having the thin copper layer formed on the surface, and dried at 100° C. for 5 minutes to obtain a film thickness. After forming a photosensitive film of 20 ⁇ m, it was exposed using a stepper (NSR1505 i6 manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m). After exposure, it was heated at 100° C. for 4 minutes.
- NSR1505 i6 manufactured by Nikon Corporation
- the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
- the temperature was raised at a rate of 10° C./min, reaching 230° C., and then maintained at 230° C. for 120 minutes to form an interlayer insulating film for rewiring layers.
- This interlayer insulating film for rewiring layer was excellent in insulating properties.
- a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.
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Abstract
Description
このような樹脂組成物を、例えば塗布等により基材に適用して感光膜を形成し、その後、必要に応じて露光、現像、加熱等を行うことにより、硬化物を基材上に形成することができる。
ポリイミド前駆体等の上記環化樹脂の前駆体は、例えば加熱により環化され、硬化物中でポリイミド等の環化樹脂となる。
樹脂組成物は、公知の塗布方法等により適用可能であるため、例えば、適用される樹脂組成物の適用時の形状、大きさ、適用位置等の設計の自由度が高いなど、製造上の適応性に優れるといえる。ポリイミド等の環化樹脂が有する高い性能に加え、このような製造上の適応性に優れる観点から、上述の樹脂組成物の産業上の応用展開がますます期待されている。
特許文献2には、下記成分(a)~(d)を含有する、樹脂組成物が記載されている。
(a)特定の構造単位を有するポリイミド前駆体
(b)活性光線照射によってラジカルを発生する化合物
(c)特定の構造を有する化合物
(d)溶剤
ここで、上記硬化物のパターンにおいて、矩形性に優れることが求められている。
硬化物のパターンが矩形性に優れるとは、硬化物が形成される基材と、硬化物の側面とのなすテーパ角が90°を超えず、かつ、パターンの断面形状がくびれた形状ではなく、テーパ角が90°に近いことをいう。
以下、硬化物のパターンが矩形性に優れることを、単に「硬化物の矩形性に優れる」ともいう。
本発明は、得られる硬化物の矩形性に優れる樹脂組成物、上記樹脂組成物を硬化してなる硬化物、上記硬化物を含む積層体、上記硬化物又は上記積層体を含む半導体デバイス、及び、矩形性に優れた硬化物が得られる硬化物の製造方法、並びに、新規な環化樹脂の前駆体を提供することを目的とする。
<1> 環化樹脂の前駆体を含み
上記環化樹脂の前駆体は、250℃に加熱した場合に塩基が発生する環化樹脂の前駆体である
樹脂組成物。
<2> 上記加熱時に、上記塩基が上記環化樹脂の前駆体から遊離する、<1>に記載の樹脂組成物。
<3> 上記環化樹脂の前駆体に含まれる塩基を発生する性質を示す構造が、非イオン性の構造である、<1>又は<2>に記載の樹脂組成物。
<4> 上記環化樹脂の前駆体に含まれる塩基を発生する性質を示す構造が、アミド結合を含む、<1>~<3>のいずれか1つに記載の樹脂組成物。
<5> 上記アミド結合が、カルボニル基側で上記環化樹脂の前駆体の主鎖と結合する、<4>に記載の樹脂組成物。
<6> 上記環化樹脂の前駆体が、下記式(1-1)で表される構造を含む、<1>~<5>のいずれか1つに記載の樹脂組成物。
<7> 光重合開始剤を更に含む、<1>~<6>のいずれか1つに記載の樹脂組成物。
<8> 重合性化合物を更に含む、<1>~<7>のいずれか1つに記載の樹脂組成物。
<9> 塩基発生剤を更に含む、<1>~<8>のいずれか1つに記載の樹脂組成物。
<10> 再配線層用層間絶縁膜の形成に用いられる、<1>~<9>のいずれか1つに記載の樹脂組成物。
<11> <1>~<10>のいずれか1つに記載の樹脂組成物を硬化してなる硬化物。
<12> <11>に記載の硬化物からなる層を2層以上含み、上記硬化物からなる層同士のいずれかの間に金属層を含む積層体。
<13> <11>に記載の硬化物又は<12>に記載の積層体を含む、半導体デバイス。
<14> 環化樹脂の前駆体を含む樹脂組成物を基材上に適用して膜を形成する膜形成工程、
上記膜を選択的に露光する工程、
上記膜を現像液を用いて現像してパターンを形成する現像工程、及び、
上記パターンを50℃以上250℃以下の温度で加熱する加熱工程を含み、
上記環化樹脂の前駆体は、上記加熱工程において塩基を生じる化合物である
硬化物の製造方法。
<15> 露光工程後、現像工程前の膜であって、現像工程後に上記パターンとして残存する膜中に存在する塩基発生基のモル数Eと、上記現像工程後の上記パターン中に存在する塩基発生基のモル数Fの比F/Eが、0.9を超える、<14>に記載の硬化物の製造方法。
<16> 上記膜形成工程において形成された上記膜において、膜の厚み方向の上部50%における塩基発生基の濃度Xと下部50%における塩基発生基の濃度Yの比X/Yが、0.90<X/Y<1.10である、<14>又は<15>に記載の硬化物の製造方法。
<17> 得られる硬化物の上記基材と接する側とは反対の側の表面における閉環率Aと上記基材と接する側の表面における閉環率Bの比A/Bが、0.90<A/B<1.10である、<14>~<16>のいずれか1つに記載の硬化物の製造方法。
<18> 現像工程において、膜厚20μm、ピッチ10μmの1:1ラインアンドスペースパターンを形成し、加熱工程において230℃で180分間加熱した場合に、ラインパターンの上端における幅収縮率Cと下端における幅収縮率Dの比C/Dが、0.90<C/D<1.10である、<14>~<17>のいずれか1つに記載の硬化物の製造方法。
<19> 下記式(2)で表される繰返し単位、式(3)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よりなる群から選ばれる、少なくとも1種の繰返し単位を含む、環化樹脂の前駆体。
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)法を用いて測定した値であり、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、及び、TSKgel Super HZ2000(以上、東ソー(株)製)を直列に連結して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。ただし、溶解性が低い場合など、溶離液としてTHFが適していない場合にはNMP(N-メチル-2-ピロリドン)を用いることもできる。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、樹脂組成物層がある場合には、基材から樹脂組成物層へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
本明細書において、特段の記載がない限り、組成物は、組成物に含まれる各成分として、その成分に該当する2種以上の化合物を含んでもよい。また、特段の記載がない限り、組成物における各成分の含有量とは、その成分に該当する全ての化合物の合計含有量を意味する。
本明細書において、特に述べない限り、温度は23℃、気圧は101,325Pa(1気圧)、相対湿度は50%RHである。
本明細書において、好ましい態様の組み合わせは、より好ましい態様である。
本発明の樹脂組成物は、環化樹脂の前駆体を含み、上記環化樹脂の前駆体は、250℃に加熱した場合に塩基が発生する環化樹脂の前駆体である。
以下、環化樹脂の前駆体であって、250℃に加熱した場合に塩基が発生する樹脂を、「特定樹脂」ともいう。
また、特定樹脂は、220℃の加熱によって塩基を発生することが好ましく、200℃の加熱によって塩基を発生する性質を示すことがより好ましく、190℃の加熱によって塩基を発生することが更に好ましく、180℃の加熱によって塩基を発生することが特に好ましい。上記塩基を発生する温度の下限は特に限定されないが、組成物の保存安定性等の観点からは、例えば、100℃以上であることが好ましい。
本発明の樹脂組成物は、例えば、半導体デバイスの絶縁膜、再配線層用層間絶縁膜、ストレスバッファ膜等の形成に用いることができ、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、本発明の樹脂組成物は、ポジ型現像に供される感光膜の形成に用いられてもよいし、ネガ型現像に供される感光膜の形成に用いられてもよい。
本発明において、ネガ型現像とは、露光及び現像において、現像により非露光部が除去される現像をいい、ポジ型現像とは、現像により露光部が除去される現像をいう。
上記露光の方法、上記現像液、及び、上記現像の方法としては、例えば、後述する硬化物の製造方法の説明における露光工程において説明された露光方法、現像工程において説明された現像液及び現像方法が使用される。
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。
ここで、本発明者らは、鋭意検討した結果、従来の塩基発生剤を用いた場合には塩基発生剤が膜内で均一に分布しにくく、得られる硬化物パターンの矩形性に劣る場合があることを見出した。
一般的に塩基発生剤は環化樹脂の前駆体等の樹脂よりも分子量が小さいため、例えば、膜の基材とは反対の側の表面に多く分布してしまう場合があり、その場合膜の基材とは反対の側の表面付近では環化が進行しやすく、膜の基材側(すなわち、膜の深部側)付近では環化が進行しにくくなると考えられる。ここで、環化樹脂の前駆体が環化すると、膜シュリンクが発生する。膜シュリンクとは、硬化前の組成物(例えば、加熱前の組成物膜)と比較して硬化後に得られる硬化物(例えば、硬化膜)の体積が減少(収縮)してしまうことをいう。例えば、上述のように、膜の基材とは反対の側の表面付近で環化が進行しやすく、膜の基材付近では環化が進行しにくい場合には、膜の基材とは反対の側の方が膜シュリンクが起こりやすく、得られる硬化物の形状は順テーパ状になる場合がある。
本発明では、環化樹脂の前駆体として、250℃に加熱した場合に塩基が発生する環化樹脂の前駆体(特定樹脂)を使用している。これにより、本発明では、塩基を発生する性質を示す構造が膜全体において均一に近い状態で分布するため、位置による膜シュリンクの度合いの差が生まれにくく、パターンの矩形性が向上すると考えられる。
更に、膜において樹脂よりも分子量の低い塩基発生剤が局所的に凝集している場合、凝集体周辺の現像液への溶解性が、凝集していない箇所(例えば、環化樹脂の前駆体など樹脂が多い箇所)における現像液への溶解性とは異なるため、現像によりパターンを形成する際のパターンのラフネス(例えば、ラインエッジラフネス、ラインワイズラフネス)が増大する場合がある。
本発明によれば、塩基を発生する性質を示す構造が膜全体において均一に近い状態で分布するため、上記ラフネスを低減することもできると推測される。
本発明の樹脂組成物は、環化樹脂の前駆体を含み、上記環化樹脂の前駆体は、250℃に加熱した場合に塩基が発生する環化樹脂の前駆体である。
環化樹脂は、主鎖構造中にイミド環構造又はオキサゾール環構造を含む樹脂であることが好ましい。
本発明において、主鎖とは、樹脂分子中で相対的に最も長い結合鎖を表す。
環化樹脂としては、ポリイミド、ポリベンゾオキサゾール、ポリアミドイミド等が挙げられる。
環化樹脂の前駆体とは、外部刺激により化学構造の変化を生じて環化樹脂となる樹脂をいい、熱により化学構造の変化を生じて環化樹脂となる樹脂が好ましく、熱により閉環反応を生じて環構造が形成されることにより環化樹脂となる樹脂がより好ましい。
環化樹脂の前駆体としては、ポリイミド前駆体、ポリベンゾオキサゾール前駆体、ポリアミドイミド前駆体等が挙げられる。
すなわち、本発明の樹脂組成物は、特定樹脂として、ポリイミド前駆体、ポリベンゾオキサゾール前駆体、及び、ポリアミドイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂(特定樹脂)を含むことが好ましい。
本発明の樹脂組成物は、特定樹脂として、ポリイミド前駆体を含むことが好ましい。
特定樹脂は、250℃に加熱した場合に塩基を発生する。
1モルの樹脂を単独で密閉容器に入れ、密閉容器中1気圧下、250℃、3時間の加熱を行った後に、HPLC(高速液体クロマトグラフィ)、で発生する塩基の量を定量し、0.01モル以上の塩基が発生している場合を「塩基が発生する」と判定することができる。上記1モルの樹脂は、液体である場合も固体である場合も、いずれも厚み0.50cm以下になるように密閉容器中に置く。上記発生量は、0.1モル以上であることが好ましく、1モル以上であることがより好ましい。上記発生量の上限は特に限定されず、例えば1000モル以下とすることができる。
得られる硬化物の破断伸び等の観点からは、特定樹脂から発生する塩基は、アミンであることが好ましく、第2級アミン又は第3級アミンであることがより好ましく、第2級アミンであることが更に好ましい。
また、特定樹脂からアミンが発生する場合、アミンは脂肪族アミンであってもよいし、芳香族アミンであってもよいが、硬化物のシュリンクを抑制する観点からは、芳香環構造を有するアミンであることが好ましい。上記芳香環構造としては、特に限定されないが、芳香族炭化水素環構造であることが好ましく、ベンゼン環構造であることがより好ましい。
発生する塩基は、共役酸のpKaが0以上である塩基が好ましく、3以上である塩基がより好ましく、6以上である塩基がより好ましい。上記共役酸のpKaの上限は特に限定されないが、30以下であることが好ましい。
pKaとは、酸から水素イオンが放出される解離反応を考え、その平衡定数Kaをその負の常用対数pKaによって表したものである。本明細書において、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。
上記共役酸のpKaが複数存在する場合、少なくとも1つが上記範囲内であることが好ましい。
上記塩基は、加熱時に塩基発生部位の開裂により環化樹脂の前駆体から遊離してもよいし、環化樹脂の前駆体の閉環に伴い環化樹脂の前駆体から遊離してもよい。
上記塩基が環化樹脂の前駆体から遊離する場合、発生する塩基の分子量は、70~500が好ましく、80~300がより好ましく、90~220が更に好ましい。
また、塩基が環化樹脂の前駆体から遊離する場合、発生する塩基の1気圧化における沸点は、50~450℃が好ましく、60~400℃がより好ましく、80~350℃が更に好ましい。
また、上記加熱時に特定樹脂に塩基が残存するものも、本発明の特定樹脂として用いることができる。
特定樹脂は、塩基を発生する性質を示す構造を含むことが好ましい。
塩基を発生する性質を示す構造としては、イオン性の構造、非イオン性の構造のいずれであってもよいが、得られる硬化物の矩形性の観点からは、非イオン性の構造であることが好ましい。
イオン性の構造としては、第4級アンモニウムカチオン構造が挙げられる。
非イオン性の構造としては、アミド結合又はウレタン結合を含む構造が挙げられる。
特定樹脂は、特定樹脂1モルに対して、塩基を発生する性質を示す構造を、1~1000モル含むことが好ましく、2~800モル含むことがより好ましく、5~500モル含むことが更に好ましい。
特定樹脂におけるアミド結合は、いわゆる(*-C(=O)NH-#)で表されるアミド結合以外に、いわゆる(*-C(=O)NR-#)で表される置換アミド結合を含む。上記*及び#はそれぞれ、他の構造との結合部位を表す。特に、*及び#のいずれもが炭素原子との結合部位であることが好ましい。
置換アミド結合における置換基(上記R)は特に限定されず、公知の置換基を用いることができ、例えばアルキル基、芳香族炭化水素基、又は、これらの組み合わせにより表される基等の炭化水素基が挙げられる。上記炭化水素基は更にハロゲン原子、アルコキシ基、アリーロキシ基、アルキルカルボニル基、アリールカルボニル基、ヒドロキシ基等により置換されていてもよい。
また、上記炭化水素基は、上記置換アミド結合における窒素原子、及び、#の部位に結合する構造のうち少なくとも一方と結合して環構造を形成してもよい。形成される環構造としては、例えば、上記アミド結合に含まれる窒素原子を環員とするピペリジン環、モルホリン環等が挙げられる。これらの環構造は更に置換基を有していてもよい。置換基としては、上記の炭化水素基における置換基と同様の基が挙げられる。
これらの中でも、発生する塩基の塩基性が高く、破断伸びを向上させやすい観点からは、特定樹脂におけるアミド結合は、置換アミド結合であることが好ましく、炭化水素基を置換基として有する置換アミド結合であることがより好ましい。
特定樹脂におけるアミド結合のカルボニル基側とは、上述の(*-C(=O)NH-#)又は(*-C(=O)NR-#)における*の側をいう。
特定樹脂は、下記式(1-1)で表される構造を含むことが好ましい。また、上述の加熱時には、式(1-1)中のアミド基が開裂して塩基を発生することが好ましい。
破断伸びの観点からは、式(1-1)中、R1はそれぞれ独立に、1価の有機基であることが好ましい。
R1は、炭化水素基であることが好ましく、アルキル基、芳香族炭化水素基、又は、これらの組み合わせにより表される基がより好ましく、炭素数1~10のアルキル基、炭素数6~20の芳香族炭化水素基、又は、これらの組み合わせにより表される基が更に好ましく、炭素数1~10のアルキル基が特に好ましい。
上記アルキル基としては、直鎖状、分岐鎖状、環状のいずれであってもよいが、破断伸び向上の観点からは、分岐鎖状のアルキル基(例えば、イソプロピル基、イソブチル基、2-エチルへキシル基等)、又は、環状のアルキル基(例えば、シクロへキシル基等)が好ましい。
R1は置換基を有していてもよく、置換基としてはハロゲン原子、アルコキシ基、アリーロキシ基、アルキルカルボニル基、アリールカルボニル基、ヒドロキシ基等が挙げられる。
2つのR1が連結して形成される環構造としては、例えば、上記アミド結合に含まれる窒素原子を環員とするピペリジン環、モルホリン環等が挙げられる。これらの環構造は更に置換基を有していてもよい。置換基としては、上記の炭化水素基における置換基と同様の基が挙げられる。
式(1-1)中、L1は特に限定されないが、炭化水素基、又は、1以上の炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)2-、及び、-NRN-よりなる群から選ばれた少なくとも1種の構造との結合により表される基が好ましい。RNは水素原子又は1価の置換基を表し、水素原子又は炭化水素基であることが好ましく、水素原子、アルキル基又は芳香族炭化水素基であることがより好ましい。
上記炭化水素基としては、飽和脂肪族炭化水素基、芳香族炭化水素基、又は、これらの結合により表される基が好ましい。
上記飽和脂肪族炭化水素基としては、炭素数1~20の飽和脂肪族炭化水素基が好ましく、炭素数1~10の飽和脂肪族炭化水素基がより好ましい。
上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が挙げられ、ベンゼン環又はナフタレン環から複数の水素原子を除いた基が好ましく、ベンゼン環から複数の水素原子を除いた基がより好ましい。
上記脂肪族炭化水素基としては、脂肪族炭化水素環基を用いてもよい。脂肪族炭化水素環基としては、特に限定されないが、ジシクロペンタン環、ボルネン環、イソボルネン環、又は、アダマンタン環から複数の水素原子を除いた基等が挙げられる。
上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が挙げられ、ベンゼン環又はナフタレン環から複数の水素原子を除いた基が好ましく、ベンゼン環から複数の水素原子を除いた基がより好ましい。
また、上記芳香族炭化水素基又は上記脂肪族炭化水素環基は、他の環と縮合していてもよい。このような態様の例としては、フタルイミド環から複数の水素原子を除いた基などが挙げられる。
得られる硬化物の破断伸び及び耐薬品性の観点からは、L1は、上記炭化水素基として芳香族炭化水素基を含むことが好ましく、ベンゼン環から複数の水素原子を除いた基を含むことがより好ましい。
また、塩基の発生効率の観点から、L1が芳香族炭化水素基を含む場合、L1における芳香族炭化水素基が式(1-1)中のヒドロキシ基と直接結合することも好ましい。L1における芳香族炭化水素基が式(1-1)中のヒドロキシ基と直接結合する場合、上記ヒドロキシ基と、L1における芳香族炭化水素基が直接または連結基を介してアミド結合と連結する部位とは、L1における芳香族炭化水素基における隣接位に存在することが好ましい。隣接位とは、芳香族炭化水素基においてある置換基が結合する環員と、別の置換基とが結合する環員とが芳香族炭化水素基における隣接する環員であることを意味しており、芳香族炭化水素基がベンゼン環である場合、オルト位であることを意味する。
また、式(1-1)中のOHは、カルボキシ基の一部分であってもよい。その場合、L1における芳香族炭化水素基が上記カルボキシ基と直接結合することも好ましい。また、L1における芳香族炭化水素基が上記カルボキシ基と直接結合する場合、上記ヒドロキシ基と、L1における芳香族炭化水素基が直接または連結基を介してアミド結合と連結する部位とは、L1における芳香族炭化水素基における隣接位に存在することが好ましい。
特定樹脂は、塩基を発生する性質を示す構造として、下記式(1-2)で表される構造を含むことも好ましい。
式(1-2)中、R1は式(1-1)中のR1と同義であり、好ましい態様も同様である。
式(1-2)中、L2は単結合又は2価の連結基を表し、単結合、又は、炭化水素基、若しくは、1以上の炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)2-、及び、-NRN-よりなる群から選ばれた少なくとも1種の構造との結合により表される基が好ましく、単結合、又は、炭化水素基、若しくは、1以上の炭化水素基と、-O-、及び、-C(=O)-よりなる群から選ばれた少なくとも1種の構造との結合により表される基がより好ましい。RNは上述の通りである。
上記炭化水素基としては、アルキレン基、2価の芳香族炭化水素基、又は、これらの結合により表される基が好ましい。
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い。
上記2価の芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が挙げられ、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い。
式(1-2)中、Cyは環構造を表す。
環構造としては、脂肪族環構造と芳香族環構造のいずれであってもよいが、芳香族環構造が好ましい。
また、炭化水素環構造と複素環構造のいずれであってもよいが、炭化水素環構造であることが好ましい。上記複素環構造に含まれる複素原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。また、上記複素環構造としては芳香族複素環構造が挙げられ、ピロール、インドール、フラン、ベンゾフラン、チオフェン、ベンゾチオフェン等が好ましく挙げられる。
塩基の発生効率の観点からは、これらの中でも、Cyは、脂肪族炭化水素環構造、又は、芳香族炭化水素環構造であることが好ましい。
上記脂肪族炭化水素環構造としては、ジシクロペンタン環、ボルネン環、イソボルネン環、アダマンタン環等が挙げられ、ジシクロペンタン環が好ましい。
上記芳香族炭化水素環構造としては、炭素数6~20の芳香族炭化水素環構造が好ましく、ベンゼン環構造又はナフタレン環構造がより好ましく、ベンゼン環構造が更に好ましい。
また、上記芳香族炭化水素環構造又は上記脂肪族炭化水素環構造は、他の環と縮合していてもよい。このような態様の例としては、フタルイミド環構造などが挙げられる。
塩基の発生効率の観点からは、これらの中でも、Cyは、ジシクロペンタン環構造、又は、ベンゼン環構造であることが好ましく、ベンゼン環構造であることがより好ましい。
また、Cyは置換基を有していてもよい。
Cyが芳香環(好ましくは、芳香族炭化水素環)である場合、塩基の発生効率の観点からは、Cyにおける式(1-2)中のヒドロキシ基との結合位置は、CyにおけるL2に対する隣接位であることが好ましい。
例えば、Cyがベンゼン環である場合、L2に対してオルト位に式(1-2)中のヒドロキシ基を有することが好ましい。
また、式(1-2)中のOHは、カルボキシ基の一部分であってもよい。Cyにおける芳香族炭化水素基が上記カルボキシ基と直接結合する場合、Cyにおける上記カルボキシ基との結合位置は、CyにおけるL2に対する隣接位であることが好ましい。
特定樹脂は、塩基を発生する性質を示す構造として、下記式(1-3)で表される構造を含むことも好ましい。
式(1-3)中、R1は上述の式(1-1)におけるR1と同義であり、好ましい態様も同様である。
式(1-3)中、R3は特に限定されないが、炭化水素基、又は、1以上の炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)2-、及び、-NRN-よりなる群から選ばれた少なくとも1種の構造との結合により表される基が好ましい。RNは上述の通りである。
上記炭化水素基としては、飽和脂肪族炭化水素基、芳香族炭化水素基、又は、これらの結合により表される基が好ましい。
上記飽和脂肪族炭化水素基としては、炭素数1~20の飽和脂肪族炭化水素基が好ましく、炭素数1~10の飽和脂肪族炭化水素基がより好ましい。
上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が挙げられ、ベンゼン環又はナフタレン環から複数の水素原子を除いた基が好ましく、ベンゼン環から複数の水素原子を除いた基がより好ましい。
上記脂肪族炭化水素基としては、脂肪族炭化水素環基を用いてもよい。脂肪族炭化水素環基としては、特に限定されないが、ジシクロペンタン環、ボルネン環、イソボルネン環、又は、アダマンタン環から複数の水素原子を除いた基等が挙げられる。
上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が挙げられ、ベンゼン環又はナフタレン環から複数の水素原子を除いた基が好ましく、ベンゼン環から複数の水素原子を除いた基がより好ましい。
また、上記芳香族炭化水素基又は上記脂肪族炭化水素環基は、他の環と縮合していてもよい。このような態様の例としては、フタルイミド環から複数の水素原子を除いた基などが挙げられる。
得られる硬化物の破断伸び及び耐薬品性の観点からは、R3は、上記炭化水素基として芳香族炭化水素基を含むことが好ましく、ベンゼン環から複数の水素原子を除いた基を含むことがより好ましい。
また、塩基の発生効率の観点から、R3が芳香族炭化水素基を含む場合、R3における芳香族炭化水素基が式(1-3)中のヒドロキシ基と直接結合することも好ましい。R3における芳香族炭化水素基が式(1-3)中のヒドロキシ基と直接結合する場合、上記ヒドロキシ基と、R3における芳香族炭化水素基が直接または連結基を介してアミド結合と連結する部位とは、R3における芳香族炭化水素基における隣接位に存在することが好ましい。隣接位とは、芳香族炭化水素基においてある置換基が結合する環員と、別の置換基とが結合する環員とが芳香族炭化水素基における隣接する環員であることを意味しており、芳香族炭化水素基がベンゼン環である場合、オルト位であることを意味する。
また、式(1-3)中のOHは、カルボキシ基の一部分であってもよい。その場合、R3における芳香族炭化水素基が上記カルボキシ基と直接結合することも好ましい。また、R3における芳香族炭化水素基が上記カルボキシ基と直接結合する場合、上記ヒドロキシ基と、R3における芳香族炭化水素基が直接または連結基を介してアミド結合と連結する部位とは、R3における芳香族炭化水素基における隣接位に存在することが好ましい。
式(1-3)中、L3は特に限定されないが、炭化水素基であることが好ましく、飽和脂肪族炭化水素基、芳香族炭化水素基、又は、これらの組み合わせにより表される基がより好ましく、炭素数1~10の飽和脂肪族炭化水素基、炭素数6~20の芳香族炭化水素基、又は、これらの組み合わせにより表される基が更に好ましく、炭素数1~10の飽和脂肪族炭化水素基が特に好ましい。
L3は置換基を有していてもよく、置換基としてはハロゲン原子、アルコキシ基、アリーロキシ基、アルキルカルボニル基、アリールカルボニル基、ヒドロキシ基等が挙げられる。
R1とL3が連結して形成される環構造としては、例えば、上記アミド結合に含まれる窒素原子を環員とするピペリジン環、モルホリン環等が挙げられる。これらの環構造は更に置換基を有していてもよい。置換基としては、上記の炭化水素基における置換基と同様の基が挙げられる。
式(1-4)中、R1が他の構造との結合部位を含まない場合、R1は式(1-1)中のR1と同義であり、好ましい態様も同様である。
式(1-4)中、R1が他の構造との結合部位を含む場合、R1は式(1-3)中のL3及び結合部位(*)と同義であり、好ましい態様も同様である。
式(1-4)中、R4が他の構造との結合部位を含まない場合、R4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)が好ましく挙げられ、水素原子又はメチル基がより好ましい。
式(1-4)中、R4が他の構造との結合部位を含む場合、R4はアルキレン基(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)、アルケニレン基(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)、アリーレン基(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)、又はこれらの結合により表される基が好ましく挙げられ、アルキレン基がより好ましい。
式(1-5)中、R5はそれぞれ独立に、1価の有機基を表し、R5のうちいずれか1つに他の構造との結合部位を含み、Aは1価以上の対アニオンを表す。
式(1-5)中、R5のうち他の構造との結合部位を含まないものは、それぞれ独立に、炭化水素基を表すことが好ましい。炭化水素基としては、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)が好ましく挙げられ、アルキル基がより好ましく、メチル基が更に好ましい。
式(1-5)中、R5のうち他の構造との結合部位を含むものは、R5は式(1-3)中のL3及び結合部位(*)と同義であり、好ましい態様も同様である。
式(1-5)中、Aは対アニオンを表す。AはpKa1が0~4のアニオンであることが好ましい。また、Aは、カルボン酸アニオン、フェノールアニオン、リン酸アニオン又は硫酸アニオンであることが好ましく、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。
上記カルボン酸アニオンは、2個以上のカルボキシル基を持つ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。
上記カルボン酸アニオンは、pKa1が4以下のカルボン酸のアニオンであることが好ましい。pKa1は、3.5以下がより好ましく、3.2以下がさらに好ましい。この態様によれば、樹脂組成物の安定性をより向上できる。
ここでpKa1とは、酸の第一解離定数の逆数の対数を表し、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値を用いることとする。
特定樹脂がラジカル重合性基を有する場合、本発明の樹脂組成物は、後述のラジカル重合開始剤を含むことが好ましく、後述のラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましい。さらに必要に応じて、後述の増感剤を含むことができる。このような本発明の樹脂組成物からは、例えば、ネガ型感光膜が形成される。
また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
特定樹脂が酸分解性基を有する場合、本発明の樹脂組成物は、後述の光酸発生剤を含むことが好ましい。このような本発明の樹脂組成物からは、例えば、化学増幅型であるポジ型感光膜又はネガ型感光膜が形成される。
本発明で用いるポリイミド前駆体は、その種類等特に定めるものではないが、下記式(2)で表される繰返し単位を含むことが好ましい。
例えば、式(2)中のR111、R113、R114及びR115よりなる群から選ばれた少なくとも1つの構造に上述の塩基を発生する性質を示す構造(好ましくは、式(1-1)で表される構造)を含むことが好ましく、式(2)中のR113及びR114よりなる群から選ばれた少なくとも1つの構造に上述の塩基を発生する性質を示す構造(好ましくは、式(1-1)で表される構造)を含むことがより好ましい。
また、特定樹脂が式(2)で表される繰返し単位を含む場合、特定樹脂は、式(2)で表される繰返し単位とは異なる箇所に塩基を発生する性質を示す構造を含んでもよい。例えば、特定樹脂の末端に塩基を発生する性質を示す構造を含む態様、特定樹脂が、式(2)で表される繰返し単位とは異なる繰返し単位であって、塩基を発生する性質を示す構造を含む繰返し単位を更に含む態様などが挙げられる。
式(2)におけるR111は、2価の有機基を表す。2価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数3~20の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基を含む基がより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく、上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。本発明の好ましい実施形態として、-Ar-および-Ar-L-Ar-で表される基であることが例示され、特に好ましくは-Ar-L-Ar-で表される基である。但し、Arは、それぞれ独立に、芳香族基であり、Lは、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-若しくは-NHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。
具体的には、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数3~20の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数6~20の芳香族基を含むジアミンであることがより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。芳香族基を含む基の例としては、下記が挙げられる。
式中、*は他の構造との結合部位を表す。
式(51)
R50~R57の1価の有機基としては、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
式(51)又は(61)の構造を与えるジアミンとしては、2,2’-ジメチルベンジジン、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4’-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等が挙げられる。これらは1種で又は2種以上を組み合わせて用いてもよい。
式(5)又は式(6)中、*はそれぞれ独立に、他の構造との結合部位を表す。
R111が塩基を発生する性質を示す構造を含む場合、例えば、R111は下記式(LD-1)で表される構造であることが好ましい。
式(LD-1)中、YD1はn+2価の有機基が好ましく、芳香族炭化水素基を含むn+2価の有機基がより好ましい。
YD1における芳香族炭化水素基は、炭素数6~30の芳香族炭化水素基であることが好ましく、炭素数6~20の芳香族炭化水素基であることがより好ましく、ベンゼン環から2以上の水素原子を除いた基であることが更に好ましく、ベンゼン環から3以上の水素原子を除いた基であることが特に好ましい。
式(LD-1)中、YD1における、式(LD-1)に記載の2つの結合部位である*との結合部位に直接結合するものは、いずれも芳香族炭化水素基であることが好ましい。すなわち、式(LD-1)に記載の2つの*は、YD1に含まれる芳香族炭化水素環構造と、直接結合することが好ましい。
また、式(LD-1)中、YD1における、PD1との結合部位は、いずれも芳香族炭化水素基であることが好ましい。すなわち、PD1は、YD1に含まれる芳香族炭化水素環構造と、直接結合することが好ましい。
式(A2-1)中、RA211~RA214がPD1との結合部位でない場合、RA211~RA214はそれぞれ独立に、水素原子、炭素数1~6のアルキル基、炭素数3~12の環状アルキル基、炭素数1~6のアルコキシ基、ヒドロキシ基、シアノ基、炭素数1~3のハロゲン化アルキル基、又は、ハロゲン原子を表すことが好ましく、溶剤溶解性の観点からは、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数1~3のハロゲン化アルキル基がより好ましく、水素原子又は炭素数1~6のアルキル基がより好ましい。
上記RA211~RA214における上記ハロゲン化アルキル基におけるハロゲン原子、又は、上記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、塩素原子又は臭素原子が好ましい。
式(A2-2)中、RA221~RA224は式(A2-1)におけるRA211~RA214とそれぞれ同義であり、好ましい態様も同様である。
式(A2-3)中、RA231~RA238はそれぞれ独立に、水素原子、炭素数1~6のアルキル基、炭素数3~12の環状アルキル基、炭素数1~6のアルコキシ基、ヒドロキシ基、シアノ基、炭素数1~3のハロゲン化アルキル基、又は、ハロゲン原子を表すことが好ましく、溶剤溶解性の観点からは、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、又は、炭素数1~3のハロゲン化アルキル基がより好ましく、水素原子又は炭素数1~6のアルキル基がより好ましい。
上記RA231~RA238における上記ハロゲン化アルキル基におけるハロゲン原子、又は、上記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、塩素原子又は臭素原子が好ましい。
式(A2-3)中、LA231は、単結合、炭素数1~6の2価の飽和炭化水素基、炭素数5~24の2価の不飽和炭化水素基、-O-、-S-、-NRN-、ヘテロ環基、又は、炭素数1~6のハロゲン化アルキレン基を表すことが好ましく、単結合、炭素数1~6の飽和炭化水素基、-O-又はヘテロ環基を表すことが好ましく、単結合又は-O-を表すことが更に好ましい。上記RNは上述の通りである。
上記2価の不飽和炭化水素基は、2価の脂肪族不飽和炭化水素基であってもよいし、2価の芳香族炭化水素基であってもよいが、2価の芳香族炭化水素基であることが好ましい。
上記ヘテロ環基としては、例えば、脂肪族又は芳香族ヘテロ環から2つの水素原子を除いた基が好ましく、脂肪族又は芳香族ヘテロ環から2つの水素原子を除いた基が好ましく、ピロリジン環、テトラヒドロフラン環、テトラヒドロチオフェン環、ピロール環、フラン環、チオフェン環、ピペリジン環、テトラヒドロピラン環、ピリジン環、モルホリン環等の環構造から2つの水素原子を除いた基がより好ましい。これらのヘテロ環は、更に他のヘテロ環又は炭化水素環と縮合環を形成していてもよい。
上記ヘテロ環の環員数は、5~10であることが好ましく、5又は6であることがより好ましい。
また、上記ヘテロ環基におけるヘテロ原子としては、酸素原子、窒素原子、又は、硫黄原子であることが好ましい。
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、塩素原子又は臭素原子が好ましい。
式(A2-4)中、RA241~RA248、LA241は式(A2-3)におけるRA231~RA238、LA231とそれぞれ同義であり、好ましい態様も同様である。
式(A2-5)中、RA251~RA258は式(A2-1)におけるRA211~RA214とそれぞれ同義であり、好ましい態様も同様である。
式(A2-2)中、RA221~RA224のうち少なくとも1つが、式(LD-1)中のPD1との結合部位であることが好ましく、RA221~RA224のうち1つが上記PD1との結合部位であることがより好ましく、RA223が上記PD1との結合部位であることが好ましい。
式(A2-3)中、RA231~RA238のうち少なくとも1つが、式(LD-1)中のPD1との結合部位であることが好ましく、RA231~RA238のうち2つが、上記PD1との結合部位であることがより好ましく、RA231~RA234のうち1つと、RA235~RA238のうち1つの計2つが上記PD1との結合部位であることが更に好ましく、RA231及びRA238の2つが、上記PD1との結合部位であることが特に好ましい。
式(A2-4)中、RA241~RA248のうち少なくとも1つが、式(LD-1)中のPD1との結合部位であることが好ましく、RA241~RA248のうち2つが、上記PD1との結合部位であることがより好ましく、RA241~RA244のうち1つと、RA245~RA248のうち1つの計2つが上記PD1との結合部位であることが更に好ましく、RA241及びRA248の2つが、上記PD1との結合部位であることが特に好ましい。
式(A2-5)中、RA251~RA258のうち少なくとも1つが、式(LD-1)中のPD1との結合部位であることが好ましく、RA251~RA258のうち2つが、上記PD1との結合部位であることがより好ましく、RA251~RA254のうち1つと、RA255~RA258のうち1つの計2つが上記PD1との結合部位であることが更に好ましく、RA253及びRA257の2つが、上記PD1との結合部位であることが特に好ましい。
式(Y-2)中、RY21~RY26、LX21はそれぞれ、式(A2-4)におけるRA242~RA247、LA241と同義であり、好ましい態様も同様である。
式(Y-1)又は式(Y-2)中、*はそれぞれ、式(2)中のR111が結合する2つの窒素原子との結合部位を、#はそれぞれ、式(LD-1)中のPD1との結合部位を、それぞれ示している。
式(LD―1)中、PD1は上述の塩基を発生する性質を示す構造を含む基を表す。
PD1は、例えば、下記式(PD-1)であることが好ましい。
LPとしては-OC(=O)-、-C(=O)O-、-C(=O)NRN-、-OC(=O)NRN-、-NRNC(=O)O-、-NRNC(=O)NRN-等が挙げられ、-O-又は-C(=O)O-が好ましい。上記RNは上述の通りである。
塩基を発生する性質を示す構造の好ましい態様は上述の通りであり、例えば、式(1-1)で表される構造、式(1-2)で表される構造などを好ましく用いることができる。
式(LD-1)中、nは1以上の整数を表し、1~10であることが好ましく、1~4がより好ましく、1又は2が更に好ましく、1が特に好ましい。
上記式(LD-1)で表される構造は、例えば、下記式(LDA-1)により表されるジアミンに由来する構造として得られる。
また、例えば、カルボキシ基等の反応性基を有するジアミンを用いて樹脂を合成し、上記反応性基と反応して共有結合を形成する構造(例えば、ヒドロキシ基等)、及び、塩基を発生する性質を示す構造を有する化合物を上記樹脂に反応させることでも、特定樹脂を合成することができる。
テトラカルボン酸二無水物は、下記式(O)で表されることが好ましい。
R115が塩基を発生する性質を示す構造を含む場合、例えば、R115は下記式(LD-2)で表される構造であることが好ましい。
式(LD-2)中、YD2はn+4価の有機基が好ましく、芳香族炭化水素基を含むn+4価の有機基がより好ましい。
YD4における芳香族炭化水素基は、炭素数6~30の芳香族炭化水素基であることが好ましく、炭素数6~20の芳香族炭化水素基であることがより好ましく、ベンゼン環から2以上の水素原子を除いた基であることが更に好ましく、ベンゼン環から3以上の水素原子を除いた基であることが特に好ましい。
式(LD-2)中、YD2における、式(LD-2)に記載の結合部位である*との結合部位に直接結合するものは、いずれも芳香族炭化水素基であることが好ましい。すなわち、式(LD-2)に記載の4つの*は、YD2に含まれる芳香族炭化水素環構造と、直接結合することが好ましい。
また、式(LD-2)中、YD2における、PD2との結合部位は、いずれも芳香族炭化水素基であることが好ましい。すなわち、PD2は、YD2に含まれる芳香族炭化水素環構造と、直接結合することが好ましい。
式(A1-1)中、RA11~RA16はそれぞれ独立に、水素原子、炭素数1~6のアルキル基、炭素数3~12の環状アルキル基、炭素数1~6のアルコキシ基、ヒドロキシ基、シアノ基、炭素数1~3のハロゲン化アルキル基、又は、ハロゲン原子を表すことが好ましく、溶剤溶解性の観点からは、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、又は、炭素数1~3のハロゲン化アルキル基がより好ましく、水素原子又は炭素数1~6のアルキル基がより好ましい。
上記RA11~RA16における上記ハロゲン化アルキル基におけるハロゲン原子、又は、上記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、塩素原子又は臭素原子が好ましい。
上記脂肪族炭化水素基としては、炭素数1~10の脂肪族炭化水素基が好ましく、炭素数1~4の脂肪族炭化水素基がより好ましい。
上記芳香族炭化水素基としては、炭素数6~10の芳香族炭化水素基が好ましく、炭素数6の芳香族炭化水素基がより好ましい。
LA1が式(LD-2)中のPD2との結合部位ではない場合、LA1は単結合、炭素数1~6の2価の飽和炭化水素基、炭素数5~24の2価の不飽和炭化水素基、-O-、-S-、-NRN-、ヘテロ環基、又は、炭素数1~6のハロゲン化アルキレン基を表すことが好ましく、単結合、炭素数1~6の飽和炭化水素基、-O-又はヘテロ環基を表すことが好ましく、単結合又は-O-を表すことが更に好ましい。上記RNは上述の通りである。
PD2は上述の式(PD-1)表される基であることが好ましい。
式(LD-2)中、mは2以上の整数を表し、1~10であることが好ましく、1~4がより好ましく、1又は2が更に好ましく、1が特に好ましい。
上記式(LD-1)で表される構造は、例えば、下記式(LDB-1)により表されるカルボン酸二無水物に由来する構造として得られる。
また、例えば、アルコキシド基等の反応性基を有するカルボン酸二無水物を用いて樹脂を合成し、上記反応性基と反応して共有結合を形成する構造(例えば、ハロゲン化アルキル基等)、及び、塩基を発生する性質を示す構造を有する化合物を上記樹脂に反応させることでも、特定樹脂を合成することができる。
特定樹脂の合成方法は、得たい特定樹脂の構造、特定樹脂の収率、合成の容易さ、原料や反応条件に係るコスト等を考慮して選択することができる。
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、イソアリル基、2-メチルアリル基、ビニル基と直接結合した芳香環を有する基(例えば、ビニルフェニル基など)、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基、下記式(III)で表される基などが挙げられ、下記式(III)で表される基が好ましい。
式(III)において、*は他の構造との結合部位を表す。
式(III)において、R201は、炭素数2~12のアルキレン基、-CH2CH(OH)CH2-、シクロアルキレン基又はポリアルキレンオキシ基を表す。
好適なR201の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基等のアルキレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基等のアルキレン基、-CH2CH(OH)CH2-、シクロヘキシル基、ポリアルキレンオキシ基がより好ましく、エチレン基、プロピレン基等のアルキレン基、又はポリアルキレンオキシ基が更に好ましい。
本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が2以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。
ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
上記アルキレン基の炭素数(アルキレン基が置換基を有する場合、置換基の炭素数を含む)は、2以上であることが好ましく、2~10であることがより好ましく、2~6であることがより好ましく、2~5であることが更に好ましく、2~4であることが一層好ましく、2又は3であることが特に好ましく、2であることが最も好ましい。
また、上記アルキレン基は、置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数(ポリアルキレンオキシ基の繰返し数)は、2~20が好ましく、2~10がより好ましく、2~6が更に好ましい。
ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰返し数の好ましい態様は上述の通りである。
酸分解性基の具体例としては、tert-ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、tert-ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。露光感度の観点からは、エトキシエチル基、又は、テトラヒドロフラニル基が好ましい。
例えば、R113及びR114の少なくとも一方が、上述の式(1-1)で表される構造、又は、上述の式(1-2)で表される構造である態様が好ましく挙げられる。
R113及びR114の少なくとも一方が、上述の塩基を発生する性質を示す構造を含む場合、特定樹脂における全てのR113及びR114に対する塩基を発生する性質を示す構造を含むR113及びR114の含有量は、0.1~100モル%であることが好ましく、0.5~50モル%であることがより好ましく、1~20モル%であることが更に好ましい。
式(2-A)
R112は、式(5)におけるR112と同義であり、好ましい範囲も同様である。
上記ポリイミド前駆体の分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上であることが更に好ましい。ポリイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。
本明細書において、分子量の分散度とは、重量平均分子量/数平均分子量により算出される値である。
また、樹脂組成物が特定樹脂として複数種のポリイミド前駆体を含む場合、少なくとも1種のポリイミド前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリイミド前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。
本発明で用いるポリベンゾオキサゾール前駆体は、その構造等について特に定めるものではないが、好ましくは下記式(3)で表される繰返し単位を含む。
例えば、式(3)中のR121、R122、R123及びR124よりなる群から選ばれた少なくとも1つの構造に上述の塩基を発生する性質を示す構造(好ましくは、式(1-1)で表される構造)を含むことが好ましく、式(3)中のR123及びR124よりなる群から選ばれた少なくとも1つの構造に上述の塩基を発生する性質を示す構造(好ましくは、式(1-1)で表される構造)を含むことがより好ましい。
また、特定樹脂が式(3)で表される繰返し単位を含む場合、特定樹脂は、式(3)で表される繰返し単位とは異なる箇所に塩基を発生する性質を示す構造を含んでもよい。
例えば、特定樹脂の末端に塩基を発生する性質を示す構造を含む態様、特定樹脂が、式(3)で表される繰返し単位とは異なる繰返し単位であって、塩基を発生する性質を示す構造を含む繰返し単位を更に含む態様などが挙げられる。
式(3)において、R121は、2価の有機基を表す。2価の有機基としては、脂肪族基及び芳香族基の少なくとも一方を含む基が好ましい。脂肪族基としては、直鎖の脂肪族基が好ましい。R121は、ジカルボン酸残基が好ましい。ジカルボン酸残基は、1種のみ用いてもよいし、2種以上用いてもよい。
脂肪族基を含むジカルボン酸としては、直鎖又は分岐(好ましくは直鎖)の脂肪族基を含むジカルボン酸が好ましく、直鎖又は分岐(好ましくは直鎖)の脂肪族基と2つの-COOHからなるジカルボン酸がより好ましい。直鎖又は分岐(好ましくは直鎖)の脂肪族基の炭素数は、2~30であることが好ましく、2~25であることがより好ましく、3~20であることが更に好ましく、4~15であることが一層好ましく、5~10であることが特に好ましい。直鎖の脂肪族基はアルキレン基であることが好ましい。
直鎖の脂肪族基を含むジカルボン酸としては、マロン酸、ジメチルマロン酸、エチルマロン酸、イソプロピルマロン酸、ジ-n-ブチルマロン酸、スクシン酸、テトラフルオロスクシン酸、メチルスクシン酸、2,2-ジメチルスクシン酸、2,3-ジメチルスクシン酸、ジメチルメチルスクシン酸、グルタル酸、ヘキサフルオログルタル酸、2-メチルグルタル酸、3-メチルグルタル酸、2,2-ジメチルグルタル酸、3,3-ジメチルグルタル酸、3-エチル-3-メチルグルタル酸、アジピン酸、オクタフルオロアジピン酸、3-メチルアジピン酸、ピメリン酸、2,2,6,6-テトラメチルピメリン酸、スベリン酸、ドデカフルオロスベリン酸、アゼライン酸、セバシン酸、ヘキサデカフルオロセバシン酸、1,9-ノナン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ヘンエイコサン二酸、ドコサン二酸、トリコサン二酸、テトラコサン二酸、ペンタコサン二酸、ヘキサコサン二酸、ヘプタコサン二酸、オクタコサン二酸、ノナコサン二酸、トリアコンタン二酸、ヘントリアコンタン二酸、ドトリアコンタン二酸、ジグリコール酸、更に下記式で表されるジカルボン酸等が挙げられる。
R122は、また、ビスアミノフェノール誘導体由来の基であることが好ましく、ビスアミノフェノール誘導体由来の基としては、例えば、3,3’-ジアミノ-4,4’-ジヒドロキシビフェニル、4,4’-ジアミノ-3,3’-ジヒドロキシビフェニル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルスルホン、ビス-(3-アミノ-4-ヒドロキシフェニル)メタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-ビス-(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)ヘキサフルオロプロパン、ビス-(4-アミノ-3-ヒドロキシフェニル)メタン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)プロパン、4,4’-ジアミノ-3,3’-ジヒドロキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジヒドロキシベンゾフェノン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルエーテル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルエーテル、1,4-ジアミノ-2,5-ジヒドロキシベンゼン、1,3-ジアミノ-2,4-ジヒドロキシベンゼン、1,3-ジアミノ-4,6-ジヒドロキシベンゼンなどが挙げられる。これらのビスアミノフェノールは、単独にて、あるいは混合して使用してもよい。
ポリベンゾオキサゾール前駆体は、閉環に伴う反りの発生を抑制できる点で、下記式(SL)で表されるジアミン残基を他の種類の繰返し単位として含むことが好ましい。
上記ポリベンゾオキサゾール前駆体の分子量の分散度は、1.4以上であることが好ましく、1.5以上がより好ましく、1.6以上であることが更に好ましい。ポリベンゾオキサゾール前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、2.6以下が好ましく、2.5以下がより好ましく、2.4以下が更に好ましく、2.3以下が一層好ましく、2.2以下がより一層好ましい。
また、樹脂組成物が特定樹脂として複数種のポリベンゾオキサゾール前駆体を含む場合、少なくとも1種のポリベンゾオキサゾール前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリベンゾオキサゾール前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。
ポリアミドイミド前駆体は、下記式(PAI-2)で表される繰返し単位を含むことが好ましい。
例えば、式(PAI-2)中のR111、R113及びR117よりなる群から選ばれた少なくとも1つの構造に上述の塩基を発生する性質を示す構造(好ましくは、式(1-1)で表される構造)を含むことが好ましく、式(PAI-2)中のR113に上述の塩基を発生する性質を示す構造(好ましくは、式(1-1)で表される構造)を含むことがより好ましい。
また、特定樹脂が式(PAI-2)で表される繰返し単位を含む場合、特定樹脂は、式(PAI-2)で表される繰返し単位とは異なる箇所に塩基を発生する性質を示す構造を含んでもよい。
例えば、特定樹脂の末端に塩基を発生する性質を示す構造を含む態様、特定樹脂が、式(PAI-2)で表される繰返し単位とは異なる繰返し単位であって、塩基を発生する性質を示す構造を含む繰返し単位を更に含む態様などが挙げられる。
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。
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。
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。
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。
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。
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。
また、本発明におけるポリアミドイミド前駆体の別の一実施形態として、式(PAI-2)で表される繰返し単位、及び、式(PAI-1)で表される繰返し単位の合計含有量が、全繰返し単位の50モル%以上である態様が挙げられる。上記合計含有量は、70モル%以上であることがより好ましく、90モル%以上であることが更に好ましく、90モル%超であることが特に好ましい。上記合計含有量の上限は、特に限定されず、末端を除くポリアミドイミド前駆体における全ての繰返し単位が、式(PAI-2)で表される繰返し単位、又は、式(PAI-1)で表される繰返し単位のいずれかであってもよい。
ポリアミドイミド前駆体の分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上であることが更に好ましい。ポリアミドイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。 また、樹脂組成物が特定樹脂として複数種のポリアミドイミド前駆体を含む場合、少なくとも1種のポリアミドイミド前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリアミドイミド前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。
ポリイミド前駆体等は、例えば、低温中でテトラカルボン酸二無水物とジアミンを反応させる方法、低温中でテトラカルボン酸二無水物とジアミンを反応させてポリアミック酸を得、縮合剤又はアルキル化剤を用いてエステル化する方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得て、その後ジアミンと縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸をハロゲン化剤を用いて酸ハロゲン化し、ジアミンと反応させる方法、などの方法を利用して得ることができる。上記製造方法のうち、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸をハロゲン化剤を用いて酸ハロゲン化し、ジアミンと反応させる方法がより好ましい。
上記縮合剤としては、例えばジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、1-エトキシカルボニル-2-エトキシ-1,2-ジヒドロキノリン、1,1-カルボニルジオキシ-ジ-1,2,3-ベンゾトリアゾール、N,N’-ジスクシンイミジルカーボネート、無水トリフルオロ酢酸等が挙げられる。
上記アルキル化剤としては、N,N-ジメチルホルムアミドジメチルアセタール、N,N-ジメチルホルムアミドジエチルアセタール、N,N-ジアルキルホルムアミドジアルキルアセタール、オルトギ酸トリメチル、オルトギ酸トリエチル等が挙げられる。
上記ハロゲン化剤としては、塩化チオニル、塩化オキサリル、オキシ塩化リン等が挙げられる。
ポリイミド前駆体等の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は1種でもよいし、2種以上でもよい。
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドン、N-エチルピロリドン、プロピオン酸エチル、ジメチルアセトアミド、ジメチルホルムアミド、テトラヒドロフラン、γ-ブチロラクトン等が例示される。
ポリイミド前駆体等の製造方法では、反応に際し、塩基性化合物を添加することが好ましい。塩基性化合物は1種でもよいし、2種以上でもよい。
塩基性化合物は、原料に応じて適宜定めることができるが、トリエチルアミン、ジイソプロピルエチルアミン、ピリジン、1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン、N,N-ジメチル-4-アミノピリジン等が例示される。
ポリイミド前駆体等の製造方法に際し、保存安定性をより向上させるため、ポリイミド前駆体等の樹脂末端に残存するカルボン酸無水物、酸無水物誘導体、或いは、アミノ基を封止することが好ましい。樹脂末端に残存するカルボン酸無水物、及び酸無水物誘導体を封止する際、末端封止剤としては、モノアルコール、フェノール、チオール、チオフェノール、モノアミン等が挙げられ、反応性、膜の安定性から、モノアルコール、フェノール類やモノアミンを用いることがより好ましい。モノアルコールの好ましい化合物としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、オクタノール、ドデシノール、ベンジルアルコール、2-フェニルエタノール、2-メトキシエタノール、2-クロロメタノール、フルフリルアルコール等の1級アルコール、イソプロパノール、2-ブタノール、シクロヘキシルアルコール、シクロペンタノール、1-メトキシ-2-プロパノール等の2級アルコール、t-ブチルアルコール、アダマンタンアルコール等の3級アルコールが挙げられる。フェノール類の好ましい化合物としては、フェノール、メトキシフェノール、メチルフェノール、ナフタレン-1-オール、ナフタレン-2-オール、ヒドロキシスチレン等のフェノール類などが挙げられる。また、モノアミンの好ましい化合物としては、アニリン、2-エチニルアニリン、3-エチニルアニリン、4-エチニルアニリン、5-アミノ-8-ヒドロキシキノリン、1-ヒドロキシ-7-アミノナフタレン、1-ヒドロキシ-6-アミノナフタレン、1-ヒドロキシ-5-アミノナフタレン、1-ヒドロキシ-4-アミノナフタレン、2-ヒドロキシ-7-アミノナフタレン、2-ヒドロキシ-6-アミノナフタレン、2-ヒドロキシ-5-アミノナフタレン、1-カルボキシ-7-アミノナフタレン、1-カルボキシ-6-アミノナフタレン、1-カルボキシ-5-アミノナフタレン、2-カルボキシ-7-アミノナフタレン、2-カルボキシ-6-アミノナフタレン、2-カルボキシ-5-アミノナフタレン、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、3-アミノ-4,6-ジヒドロキシピリミジン、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール、2-アミノチオフェノール、3-アミノチオフェノール、4-アミノチオフェノールなどが挙げられる。これらを2種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。
また、樹脂末端のアミノ基を封止する際、アミノ基と反応可能な官能基を有する化合物で封止することが可能である。アミノ基に対する好ましい封止剤は、カルボン酸無水物、カルボン酸クロリド、カルボン酸ブロミド、スルホン酸クロリド、無水スルホン酸、スルホン酸カルボン酸無水物などが好ましく、カルボン酸無水物、カルボン酸クロリドがより好ましい。カルボン酸無水物の好ましい化合物としては、無水酢酸、無水プロピオン酸、無水シュウ酸、無水コハク酸、無水マレイン酸、無水フタル酸、無水安息香酸、5-ノルボルネン-2,3-ジカルボン酸無水物などが挙げられる。また、カルボン酸クロリドの好ましい化合物としては、塩化アセチル、アクリル酸クロリド、プロピオニルクロリド、メタクリル酸クロリド、ピバロイルクロリド、シクロヘキサンカルボニルクロリド、2-エチルヘキサノイルクロリド、シンナモイルクロリド、1-アダマンタンカルボニルクロリド、ヘプタフルオロブチリルクロリド、ステアリン酸クロリド、ベンゾイルクロリド、などが挙げられる。
このような末端封止剤としては、例えば、塩基を発生する性質を示す構造と、ヒドロキシ基、チオール基、アミノ基、カルボキシ基、カルボン酸無水物域、カルボン酸ハライド基、スルホン酸無水物基、スルホン酸ハライド基、又は、スルホン酸カルボン酸無水物基等の反応性基を有する化合物を用いることができる。
末端封止剤としては、例えば、1以上の塩基を発生する性質を示す構造と、1つの上記反応性基とを有する化合物を用いることができる。
塩基を発生する性質を示す構造の好ましい態様は、上述の通りである。
ポリイミド前駆体等の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中に共存している脱水縮合剤の吸水副生物を必要に応じて濾別した後、水、脂肪族低級アルコール、又はその混合液等の貧溶媒に、得られた重合体成分を投入し、重合体成分を析出させることで、固体として析出させ、乾燥させることでポリイミド前駆体等を得ることができる。精製度を向上させるために、ポリイミド前駆体等を再溶解、再沈析出、乾燥等の操作を繰返してもよい。さらに、イオン交換樹脂を用いてイオン性不純物を除去する工程を含んでいてもよい。
特定樹脂の具体例としては、特に限定されないが、後述の実施例において使用した特定樹脂が好ましく挙げられる。
本発明の樹脂組成物における特定樹脂の含有量は、樹脂組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明の樹脂組成物における樹脂の含有量は、樹脂組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
本発明の樹脂組成物は、特定樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
具体的には、本発明の樹脂組成物は、特定樹脂と、後述する他の樹脂とを合計で2種以上含んでもよいし、特定樹脂を2種以上含んでいてもよいが、特定樹脂を2種以上含むことが好ましい。
本発明の樹脂組成物が特定樹脂を2種以上含む場合、例えば、ポリイミド前駆体であって、二無水物由来の構造(上述の式(2)でいうR115)が異なる2種以上のポリイミド前駆体を含むことが好ましい。
本発明の樹脂組成物は、上述した特定樹脂と、特定樹脂とは異なる他の樹脂(以下、単に「他の樹脂」ともいう)とを含んでもよい。
他の樹脂としては、ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体、ポリベンゾオキサゾール、ポリアミドイミド前駆体、ポリアミドイミド、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、(メタ)アクリル樹脂、(メタ)アクリルアミド樹脂、ウレタン樹脂、ブチラール樹脂、スチリル樹脂、ポリエーテル樹脂、ポリエステル樹脂等が挙げられる。
上記ポリイミド前駆体、ポリベンゾオキサゾール前駆体、ポリアミドイミド前駆体としては、塩基を発生する性質を示す構造を有しない以外は上述の特定樹脂と同様の樹脂を使用することができる。
また、上記ポリイミド、ポリベンゾオキサゾール、ポリアミドイミドとしては、上述の特定樹脂を閉環させたもの、又は、塩基を発生する性質を示す構造を有しない以外は上述の特定樹脂と同様の樹脂を閉環させたものを用いることができる。その際、溶剤への溶解性等を考慮して、構造を一部変更してもよい。
例えば、(メタ)アクリル樹脂を更に加えることにより、塗布性に優れた樹脂組成物が得られ、また、耐溶剤性に優れたパターン(硬化物)が得られる。
例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が20,000以下の重合性基価の高い(例えば、樹脂1gにおける重合性基の含有モル量が1×10-3モル/g以上である)(メタ)アクリル樹脂を樹脂組成物に添加することにより、樹脂組成物の塗布性、パターン(硬化物)の耐溶剤性等を向上させることができる。
また、本発明の樹脂組成物における、他の樹脂の含有量は、樹脂組成物の全固形分に対し、80質量%以下であることが好ましく、75質量%以下であることがより好ましく、70質量%以下であることが更に好ましく、60質量%以下であることが一層好ましく、50質量%以下であることがより一層好ましい。
また、本発明の樹脂組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、樹脂組成物の全固形分に対し、20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが一層好ましく、1質量%以下であることがより一層好ましい。上記含有量の下限は特に限定されず、0質量%以上であればよい。
本発明の樹脂組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本発明の樹脂組成物は、耐薬品性の観点から、有機金属錯体を含んでもよい。
有機金属錯体とは、金属原子を含む有機錯体化合物であればよいが、金属原子及び有機基を含む錯体化合物であることが好ましく、金属原子に対して有機基が配位した化合物であることがより好ましく、メタロセン化合物であることが更に好ましい。
本発明において、メタロセン化合物とは、置換基を有してもよいシクロペンタジエニルアニオン誘導体2個をη5-配位子として有する有機金属錯体をいう。
上記有機基としては、特に限定されないが、炭化水素基、又は、炭化水素基とヘテロ原子との組み合わせからなる基が好ましい。ヘテロ原子としては、酸素原子、硫黄原子、窒素原子が好ましい。
本発明では、有機基の少なくとも1つは環状基であることが好ましく、少なくとも2つは環状基であることがより好ましい。
上記環状基は、5員環の環状基及び6員環の環状基から選択されることが好ましく、5員環の環状基であることがより好ましい。
上記環状基は、炭化水素環でも複素環でもよいが、炭化水素環が好ましい。
5員環の環状基としては、シクロペンタジエニル基が好ましい。
また、本発明で用いる有機金属錯体は、1分子中に2~4個の環状基を含むことが好ましい。
本発明において、光ラジカル重合開始能を有するとは、光の照射によりラジカル重合を開始させることのできるフリーラジカルを発生させることができることを意味する。例えば、ラジカル架橋剤と有機金属錯体とを含む組成物に対して、有機金属錯体が光を吸収する波長域であって、ラジカル架橋剤が光を吸収しない波長域の光を照射した時に、ラジカル架橋剤の消失の有無を確認することにより光ラジカル重合開始能の有無を確認することができる。消失の有無を確認するには、ラジカル架橋剤の種類に応じて適宜の方法を選択できるが、例えばIR測定(赤外分光測定)又はHPLC測定(高速液体クロマトグラフィ)により確認すればよい。
有機金属錯体が光ラジカル重合開始能を有する場合、有機金属錯体はメタロセン化合物であることが好ましく、チタノセン化合物、ジルコノセン化合物又はハフノセン化合物であることがより好ましく、チタノセン化合物、又は、ジルコノセン化合物であることが更に好ましく、チタノセン化合物であることが特に好ましい。
有機金属錯体が光ラジカル重合開始能を有しない場合、有機金属錯体は、チタノセン化合物、テトラアルコキシチタン化合物、チタンアシレート化合物、チタンキレート化合物、ジルコノセン化合物及びハフノセン化合物よりなる群から選択された少なくとも1種の化合物であることが好ましく、チタノセン化合物、ジルコノセン化合物及びハフノセン化合物よりなる群から選択された少なくとも1種の化合物であることがより好ましく、チタノセン化合物及びジルコノセン化合物よりなる群から選択された少なくとも1種の化合物であることが更に好ましく、チタノセン化合物であることが特に好ましい。
上記Rは、それぞれ独立に、芳香族基、アルキル基、ハロゲン原子及びアルキルスルホニルオキシ基から選択されることが好ましい。
式(P)中のRにおける芳香族基としては、炭素数6~20の芳香族基が挙げられ、炭素数6~20の芳香族炭化水素基が好ましく、フェニル基、1-ナフチル基、又は、2-ナフチル基等が挙げられる。
式(P)中のRにおける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1~10のアルキル基がより好ましく、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、t-ブチル基、イソペンチル基、2-エチルヘキシル基、2-メチルヘキシル基、シクロペンチル基等が挙げられる。
上記Rにおけるハロゲン原子としては、F、Cl、Br、Iが挙げられる。
上記Rにおけるアルキルスルホニルオキシ基を構成する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1~10のアルキル基がより好ましく、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、t-ブチル基、イソペンチル基、2-エチルヘキシル基、2-メチルヘキシル基、シクロペンチル基等が挙げられる。
上記Rは、更に置換基を有していてもよい。置換基の例としては、ハロゲン原子(F、Cl、Br、I)、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、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、モノアルキルアミノ基、ジアルキルアミノ基、モノアリールアミノ基及びジアリールアミノ基等が挙げられる。
有機金属錯体は、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。
本発明の樹脂組成物は、重合性化合物を含むことが好ましい。
重合性化合物としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。
本発明の樹脂組成物は、ラジカル架橋剤を含むことが好ましい。
ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基、マレイミド基、(メタ)アクリルアミド基などのエチレン性不飽和結合を有する基が挙げられる。
これらの中でも、上記エチレン性不飽和結合を含む基としては、(メタ)アクリロイル基、(メタ)アクリルアミド基、ビニルフェニル基が好ましく、反応性の観点からは、(メタ)アクリロイル基がより好ましい。
上記エチレン性不飽和結合を2個以上有する化合物としては、エチレン性不飽和結合を2~15個有する化合物が好ましく、エチレン性不飽和結合を2~10個有する化合物がより好ましく、2~6個有する化合物が更に好ましい。
また、得られるパターン(硬化物)の膜強度の観点からは、本発明の樹脂組成物は、エチレン性不飽和結合を2個有する化合物と、上記エチレン性不飽和結合を3個以上有する化合物とを含むことも好ましい。
具体的な化合物としては、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、PEG(ポリエチレングリコール)200ジアクリレート、PEG200ジメタクリレート、PEG600ジアクリレート、PEG600ジメタクリレート、ポリテトラエチレングリコールジアクリレート、ポリテトラエチレングリコールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、3-メチル-1,5-ペンタンジオールジアクリレート、1,6-ヘキサンジオールジアクリレート、1,6ヘキサンジオールジメタクリレート、ジメチロール-トリシクロデカンジアクリレート、ジメチロール-トリシクロデカンジメタクリレート、ビスフェノールAのEO(エチレンオキシド)付加物ジアクリレート、ビスフェノールAのEO付加物ジメタクリレート、ビスフェノールAのPO(プロピレンオキシド)付加物ジアクリレート、ビスフェノールAのPO付加物ジメタクリレート、2-ヒドロキシー3-アクリロイロキシプロピルメタクリレート、イソシアヌル酸EO変性ジアクリレート、イソシアヌル酸変性ジメタクリレート、その他ウレタン結合を有する2官能アクリレート、ウレタン結合を有する2官能メタクリレートを使用することができる。これらは必要に応じ、2種以上を混合し使用することができる。
なお、例えばPEG200ジアクリレートとは、ポリエチレングリコールジアクリレートであって、ポリエチレングリコール鎖の式量が200程度のものをいう。
本発明の樹脂組成物は、パターン(硬化物)の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、グリシジル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸誘導体、N-ビニルピロリドン、N-ビニルカプロラクタム等のN-ビニル化合物類、アリルグリシジルエーテル等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で100℃以上の沸点を持つ化合物も好ましい。
その他、2官能以上のラジカル架橋剤としては、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類が挙げられる。
本発明の樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことも好ましい。
本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の光酸発生剤、又は、光塩基発生剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
上記酸又は塩基は、露光工程において、光酸発生剤又は光塩基発生剤から発生する酸又は塩基であることが好ましい。
他の架橋剤としては、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基を有する化合物が好ましく、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をアシルオキシメチル基、メチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
これらの中でも、本発明の樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことがより好ましい。
上記化合物が有するアルコキシメチル基又はアシルオキシメチル基は、炭素数2~5が好ましく、炭素数2又は3が好ましく、炭素数2がより好ましい。
上記化合物が有するアルコキシメチル基及びアシルオキシメチル基の総数は1~10が好ましく、より好ましくは2~8、特に好ましくは3~6である。
上記化合物の分子量は好ましくは1500以下であり、180~1200が好ましい。
R101及びR102は、それぞれ独立に、一価の有機基を表し、互いに結合して環を形成してもよい。
R105は各々独立にアルキル基又はアルケニル基を示し、a、b及びcは各々独立に1~3であり、dは0~4であり、eは0~3であり、fは0~3であり、a+dは5以下であり、b+eは4以下であり、c+fは4以下である。
酸の作用により分解し、アルカリ可溶性基を生じる基、酸の作用により脱離する基、-C(R4)2COOR5で表される基におけるR5については、例えば、-C(R36)(R37)(R38)、-C(R36)(R37)(OR39)、-C(R01)(R02)(OR39)等を挙げることができる。
式中、R36~R39は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。
上記アルキル基としては、炭素数1~10のアルキル基が好ましく、炭素数1~5のアルキル基がより好ましい。
上記アルキル基は、直鎖状、分岐鎖状のいずれであってもよい。
上記シクロアルキル基としては、炭素数3~12のシクロアルキル基が好ましく、炭素数3~8のシクロアルキル基がより好ましい。
上記シクロアルキル基は単環構造であってもよいし、縮合環等の多環構造であってもよい。
上記アリール基は炭素数6~30の芳香族炭化水素基であることが好ましく、フェニル基であることがより好ましい。
上記アラルキル基としては、炭素数7~20のアラルキル基が好ましく、炭素数7~16のアラルキル基がより好ましい。
上記アラルキル基はアルキル基により置換されたアリール基を意図しており、これらのアルキル基及びアリール基の好ましい態様は、上述のアルキル基及びアリール基の好ましい態様と同様である。
上記アルケニル基は炭素数3~20のアルケニル基が好ましく、炭素数3~16のアルケニル基がより好ましい。
また、これらの基は本発明の効果が得られる範囲内で、公知の置換基を更に有していてもよい。
耐熱性の観点で、アルコキシメチル基又はアシルオキシメチル基が、直接芳香環やトリアジン環上に置換した化合物が好ましい。
ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
1,3-ジ(メトキシメチル)4,5-ジヒドロキシ-2-イミダゾリジノン、1,3-ジ(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリジノンなどが挙げられる。
このような化合物の具体例としては、ベンゼンジメタノール、ビス(ヒドロキシメチル)クレゾール、ビス(ヒドロキシメチル)ジメトキシベンゼン、ビス(ヒドロキシメチル)ジフェニルエーテル、ビス(ヒドロキシメチル)ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス(ヒドロキシメチル)ビフェニル、ジメチルビス(ヒドロキシメチル)ビフェニル、ビス(メトキシメチル)ベンゼン、ビス(メトキシメチル)クレゾール、ビス(メトキシメチル)ジメトキシベンゼン、ビス(メトキシメチル)ジフェニルエーテル、ビス(メトキシメチル)ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス(メトキシメチル)ビフェニル、ジメチルビス(メトキシメチル)ビフェニル、4,4’,4’’-エチリデントリス[2,6-ビス(メトキシメチル)フェノール]、5,5’-[2,2,2‐トリフルオロ‐1‐(トリフルオロメチル)エチリデン]ビス[2‐ヒドロキシ‐1,3‐ベンゼンジメタノール]、3,3’,5,5’-テトラキス(メトキシメチル)-1,1’-ビフェニル-4,4’-ジオール等が挙げられる。
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、本発明の樹脂組成物の低温硬化及び反りの抑制に効果的である。
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)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。
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。
本発明の樹脂組成物は、光及び/又は熱により重合を開始させることができる重合開始剤を含むことが好ましい。特に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。
RX2は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
RX3~RX14は、それぞれ独立して水素原子または置換基を表す。
ただし、RX10~RX14のうち少なくとも一つは、電子求引性基である。
なお、光重合開始剤は熱重合開始剤としても機能する場合があるため、オーブンやホットプレート等の加熱によって光重合開始剤による架橋を更に進行させられる場合がある。
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。
使用可能な増感剤として、ベンゾフェノン系、ミヒラーズケトン系、クマリン系、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アントラセン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ペンゾピラン系、インジゴ系等の化合物を使用することができる。
増感剤としては、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン(7-(ジエチルアミノ)クマリン-3-カルボン酸エチル)、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンゾチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン、ジフェニルアセトアミド、ベンズアニリド、N-メチルアセトアニリド、3‘,4’-ジメチルアセトアニリド等が挙げられる。
また、他の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。
本発明の樹脂組成物は、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-S-S-、-SO2-S-、-N-O-、SH、PH、SiH、及びGeHを有する化合物群、RAFT(Reversible Addition Fragmentation chain Transfer)重合に用いられるチオカルボニルチオ基を有するジチオベンゾアート、トリチオカルボナート、ジチオカルバマート、キサンタート化合物等が用いられる。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。
本発明の樹脂組成物は、塩基発生剤を含んでもよい。ここで、塩基発生剤とは、物理的または化学的な作用によって塩基を発生することができる化合物である。本発明の樹脂組成物にとって好ましい塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。
特に、樹脂組成物が環化樹脂の前駆体を含む場合、樹脂組成物は塩基発生剤を含むことが好ましい。樹脂組成物が熱塩基発生剤を含有することによって、例えば加熱により前駆体の環化反応を促進でき、硬化物の機械特性や耐薬品性が良好なものとなり、例えば半導体パッケージ中に含まれる再配線層用層間絶縁膜としての性能が良好となる。
塩基発生剤としては、イオン型塩基発生剤でもよく、非イオン型塩基発生剤でもよい。塩基発生剤から発生する塩基としては、例えば、2級アミン、3級アミンが挙げられる。
本発明に係る塩基発生剤について特に制限はなく、公知の塩基発生剤を用いることができる。公知の塩基発生剤としては、例えば、カルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール誘導体化合物、アミンイミド化合物、ピリジン誘導体化合物、α-アミノアセトフェノン誘導体化合物、4級アンモニウム塩誘導体化合物、ピリジニウム塩、α-ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド誘導体化合物、アシルオキシイミノ化合物、などを用いることができる。
非イオン型塩基発生剤の具体的な化合物としては、式(B1)、式(B2)、又は式(B3)で表される化合物が挙げられる。
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。
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。
環状アルキル基は、炭素数3~12のものが好ましく、3~6がより好ましい。環状アルキル基は、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基等が挙げられる。
鎖状アルキル基と環状アルキル基の組合せに係る基は、炭素数4~24のものが好ましく、4~18がより好ましく、4~12がさらに好ましい。鎖状アルキル基と環状アルキル基の組合せに係る基は、例えば、シクロヘキシルメチル基、シクロヘキシルエチル基、シクロヘキシルプロピル基、メチルシクロヘキシルメチル基、エチルシクロヘキシルエチル基等が挙げられる。
酸素原子を鎖中に有するアルキル基は、炭素数2~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。酸素原子を鎖中に有するアルキル基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。
なかでも、後述する分解生成塩基の沸点を高める観点で、RN1およびRN2は炭素数5~12のアルキル基が好ましい。ただし、金属(例えば銅)の層と積層する際の密着性を重視する処方においては、環状のアルキル基を有する基や炭素数1~8のアルキル基であることが好ましい。
2価の炭化水素連結基は、炭素数1~24のものが好ましく、2~12がより好ましく、2~6がさらに好ましい。2価の脂肪族炭化水素基は、炭素数1~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。2価の芳香族炭化水素基は、炭素数6~22のものが好ましく、6~18がより好ましく、6~10がさらに好ましい。2価の脂肪族炭化水素基と2価の芳香族炭化水素基の組み合わせに係る基(例えば、アリーレンアルキル基)は、炭素数7~22のものが好ましく、7~18がより好ましく、7~10がさらに好ましい。
直鎖または分岐の鎖状アルキレン基は、炭素数1~12のものが好ましく、2~6がより好ましく、2~4がさらに好ましい。
環状アルキレン基は、炭素数3~12のものが好ましく、3~6がより好ましい。
鎖状アルキレン基と環状アルキレン基の組み合わせに係る基は、炭素数4~24のものが好ましく、4~12がより好ましく、4~6がさらに好ましい。
酸素原子を鎖中に有するアルキレン基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。酸素原子を鎖中に有するアルキレン基は、炭素数1~12のものが好ましく、1~6がより好ましく、1~3がさらに好ましい。
環状のアルケニレン基は、炭素数3~12のものが好ましく、3~6がより好ましい。環状のアルケニレン基は、C=C結合の数は1~6が好ましく、1~4がより好ましく、1~2がさらに好ましい。
アリーレン基は、炭素数6~22のものが好ましく、6~18がより好ましく、6~10がさらに好ましい。
アリーレンアルキレン基は、炭素数7~23のものが好ましく、7~19がより好ましく、7~11がさらに好ましい。
中でも、鎖状アルキレン基、環状アルキレン基、酸素原子を鎖中に有するアルキレン基、鎖状のアルケニレン基、アリーレン基、アリーレンアルキレン基が好ましく、1,2-エチレン基、プロパンジイル基(特に1,3-プロパンジイル基)、シクロヘキサンジイル基(特に1,2-シクロヘキサンジイル基)、ビニレン基(特にシスビニレン基)、フェニレン基(1,2-フェニレン基)、フェニレンメチレン基(特に1,2-フェニレンメチレン基)、エチレンオキシエチレン基(特に1,2-エチレンオキシ-1,2-エチレン基)がより好ましい。
塩基発生剤は、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。
本発明の樹脂組成物は、溶剤を含むことが好ましい。
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、環状炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。
本発明の樹脂組成物は、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、アルコキシシリル基を有するシランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等が挙げられる。
シランカップリング剤としては、例えば、国際公開第2015/199219号の段落0167に記載の化合物、特開2014-191002号公報の段落0062~0073に記載の化合物、国際公開第2011/080992号の段落0063~0071に記載の化合物、特開2014-191252号公報の段落0060~0061に記載の化合物、特開2014-041264号公報の段落0045~0052に記載の化合物、国際公開第2014/097594号の段落0055に記載の化合物、特開2018-173573の段落0067~0078に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。また、特開2011-128358号公報の段落0050~0058に記載のように異なる2種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Meはメチル基を、Etはエチル基を表す。
アルミニウム系接着助剤としては、例えば、アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。
本発明の樹脂組成物は、マイグレーション抑制剤を更に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膜内へ移動することを効果的に抑制可能となる。
本発明の樹脂組成物は、重合禁止剤を含むことが好ましい。重合禁止剤としてはフェノール系化合物、キノン系化合物、アミノ系化合物、N-オキシルフリーラジカル化合物系化合物、ニトロ系化合物、ニトロソ系化合物、ヘテロ芳香環系化合物、金属化合物などが挙げられる。
本発明の樹脂組成物は、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、本分野において公知の光酸発生剤、界面活性剤、高級脂肪酸誘導体、熱重合開始剤、無機粒子、紫外線吸収剤、有機チタン化合物、酸化防止剤、凝集防止剤、フェノール系化合物、他の高分子化合物、可塑剤及びその他の助剤類(例えば、消泡剤、難燃剤など)等を配合することができる。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。これらの添加剤を配合する場合、その合計配合量は本発明の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。
界面活性剤としては、フッ素系界面活性剤、シリコーン系界面活性剤、炭化水素系界面活性剤などの各種界面活性剤を使用できる。界面活性剤はノニオン型界面活性剤であってもよく、カチオン型界面活性剤であってもよく、アニオン型界面活性剤であってもよい。
フッ素系界面活性剤は、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができ、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報の段落0050~0090および段落0289~0295に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。また、市販品としては、例えばDIC(株)製のメガファックRS-101、RS-102、RS-718K等が挙げられる。
界面活性剤の含有量は、組成物の全固形分に対して、0.001~2.0質量%が好ましく、0.005~1.0質量%がより好ましい。
本発明の樹脂組成物は、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本発明の樹脂組成物の表面に偏在させてもよい。
本発明の樹脂組成物は、熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。熱ラジカル重合開始剤を添加することによって樹脂及び重合性化合物の重合反応を進行させることもできるので、より耐溶剤性を向上できる。また、上述した光重合開始剤も熱により重合を開始する機能を有する場合があり、熱重合開始剤として添加することができる場合がある。
本発明の樹脂組成物は、無機粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。
無機粒子の上記平均粒子径は、一次粒子径であり、また体積平均粒子径である。体積平均粒子径は、Nanotrac WAVE II EX-150(日機装社製)による動的光散乱法で測定できる。
上記測定が困難である場合は、遠心沈降光透過法、X線透過法、レーザー回折・散乱法で測定することもできる。
本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、p-オクチルフェニルサリシレート、p-t-ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-アミル-5’-イソブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-プロピルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-[2’-ヒドロキシ-5’-(1,1,3,3-テトラメチル)フェニル]ベンゾトリアゾールなどが挙げられる。
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、0.001質量%以上1質量%以下であることが好ましく、0.01質量%以上0.1質量%以下であることがより好ましい。
本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。
有機チタン化合物の具体例を、以下のI)~VII)に示す:
I)チタンキレート化合物:中でも、樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を2個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n-ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2-エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n-ノニロキサイド)、チタニウムテトラ(n-プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2-(アリロキシメチル)ブトキサイド}]等である。
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。
本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。上述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物を使用することもでき、この内容は本明細書に組み込まれる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
好ましい酸化防止剤の例としては、2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノールおよび式(3)で表される化合物が挙げられる。
本実施形態の樹脂組成物は、必要に応じて凝集防止剤を含有してもよい。凝集防止剤としては、ポリアクリル酸ナトリウム等が挙げられる。
本発明の組成物は、凝集防止剤を含んでも含まなくてもよいが、含む場合、凝集防止剤の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上10質量%以下であることが好ましく、0.02質量%以上5質量%以下であることがより好ましい。
本実施形態の樹脂組成物は、必要に応じてフェノール系化合物を含有してもよい。フェノール系化合物としては、Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisP-OCHP、メチレントリス-FR-CR、BisRS-26X(以上、商品名、本州化学工業(株)製)、BIP-PC、BIR-PC、BIR-PTBP、BIR-BIPC-F(以上、商品名、旭有機材工業(株)製)等が挙げられる。
本発明の組成物は、フェノール系化合物を含んでも含まなくてもよいが、含む場合、フェノール系化合物の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上30質量%以下であることが好ましく、0.02質量%以上20質量%以下であることがより好ましい。
他の高分子化合物としては、シロキサン樹脂、(メタ)アクリル酸を共重合した(メタ)アクリルポリマー、ノボラック樹脂、レゾール樹脂、ポリヒドロキシスチレン樹脂およびそれらの共重合体などが挙げられる。他の高分子化合物はメチロール基、アルコキシメチル基、エポキシ基などの架橋基が導入された変性体であってもよい。
本発明の組成物は、他の高分子化合物を含んでも含まなくてもよいが、含む場合、他の高分子化合物の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上30質量%以下であることが好ましく、0.02質量%以上20質量%以下であることがより好ましい。
本発明の樹脂組成物の粘度は、樹脂組成物の固形分濃度により調整できる。塗布膜厚の観点から、1,000mm2/s~12,000mm2/sが好ましく、2,000mm2/s~10,000mm2/sがより好ましく、2,500mm2/s~8,000mm2/sが更に好ましい。上記範囲であれば、均一性の高い塗布膜を得ることが容易になる。1,000mm2/s以上であれば、例えば再配線用絶縁膜として必要とされる膜厚で塗布することが容易であり、12,000mm2/s以下であれば、塗布面状に優れた塗膜が得られる。
本発明の樹脂組成物の含水率は、2.0質量%未満であることが好ましく、1.5質量%未満であることがより好ましく、1.0質量%未満であることが更に好ましい。2.0%未満であれば、樹脂組成物の保存安定性が向上する。
水分の含有量を維持する方法としては、保管条件における湿度の調整、保管時の収容容器の空隙率低減などが挙げられる。
ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。
本発明の樹脂組成物を硬化することにより、この樹脂組成物の硬化物を得ることができる。
本発明の硬化物は、本発明の樹脂組成物を硬化してなる硬化物である。
樹脂組成物の硬化は加熱によるものであることが好ましく、加熱温度が120℃~400℃の範囲内であることがより好ましく、140℃~380℃の範囲内にあることが更に好ましく、170℃~350℃の範囲内にあることが特に好ましい。樹脂組成物の硬化物の形態は、特に限定されず、フィルム状、棒状、球状、ペレット状など、用途に合わせて選択することができる。本発明において、この硬化物は、フィルム状であることが好ましい。また、樹脂組成物のパターン加工によって、壁面への保護膜の形成、導通のためのビアホール形成、インピーダンスや静電容量あるいは内部応力の調整、放熱機能付与など、用途にあわせて、この硬化物の形状を選択することもできる。この硬化物(硬化物からなる膜)の膜厚は、0.5μm以上150μm以下であることが好ましい。
本発明の樹脂組成物を硬化した際の収縮率は、50%以下が好ましく、45%以下がより好ましく、40%以下が更に好ましい。ここで、収縮率は、樹脂組成物の硬化前後の体積変化の百分率を指し、下記の式より算出することができる。
収縮率[%]=100-(硬化後の体積÷硬化前の体積)×100
本発明の樹脂組成物の硬化物のイミド化反応率は、70%以上が好ましく、80%以上がより好ましく、90%以上が更に好ましい。70%以上であれば、機械特性に優れた硬化物となる場合がある。
本発明の樹脂組成物の硬化物の破断伸びは、30%以上が好ましく、40%以上がより好ましく、50%以上が更に好ましい。
本発明の樹脂組成物の硬化物のガラス転移温度(Tg)は、180℃以上であることが好ましく、210℃以上であることがより好ましく、230℃以上であることがさらに好ましい。
本発明の樹脂組成物は、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。
混合は撹拌羽による混合、ボールミルによる混合、タンク自身を回転させる混合などを採用することができる。
混合中の温度は10~30℃が好ましく、15~25℃がより好ましい。
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。
更にフィルターを用いたろ過後、ボトルに充填した樹脂組成物を減圧下に置き、脱気する工程を施しても良い。
本発明の硬化物の製造方法は、環化樹脂の前駆体を含む樹脂組成物を基材上に適用して膜を形成する膜形成工程、上記膜を選択的に露光する工程、上記膜を現像液を用いて現像してパターンを形成する現像工程、及び、上記パターンを50℃以上250℃以下の温度で加熱する加熱工程を含み、上記環化樹脂の前駆体は、上記加熱工程において塩基を生じる化合物である。
本発明の硬化物の製造方法において用いられる環化樹脂の前駆体としては、上述の本発明の樹脂組成物に含まれる特定樹脂が好ましく挙げられる。
また、本発明の硬化物の製造方法に係る膜形成工程において用いられる樹脂組成物は、上述の本発明の樹脂組成物であることが好ましい。
本発明の樹脂組成物は、基材上に適用して膜を形成する膜形成工程に用いることができる。
本発明の硬化物の製造方法は、樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む。
基材の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基材、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ni、Cu、Cr、Feなどの金属基材(例えば、金属から形成された基材、及び、金属層が例えばめっきや蒸着等により形成された基材のいずれであってもよい)、紙、SOG(Spin On Glass)、TFT(薄膜トランジスタ)アレイ基材、モールド基材、プラズマディスプレイパネル(PDP)の電極板などが挙げられ、特に制約されない。本発明では、特に、半導体作製基材が好ましく、シリコン基材、Cu基材およびモールド基材がより好ましい。
また、これらの基材にはヘキサメチルジシラザン(HMDS)等による密着層や酸化層などの層が表面に設けられていてもよい。
また、基材の形状は特に限定されず、円形状であってもよく、矩形状であってもよい。
基材のサイズとしては、円形状であれば、例えば直径が100~450mmであり、好ましくは200~450mmである。矩形状であれば、例えば短辺の長さが100~1000mmであり、好ましくは200~700mmである。
また、基材としては、例えば板状、好ましくはパネル状の基材(基板)が用いられる。
また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス(EBR)、バックリンスなどが挙げられる。
また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。
上記膜は、膜形成工程(層形成工程)の後に、溶剤を除去するために形成された膜(層)を乾燥する工程(乾燥工程)に供されてもよい。
すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を乾燥する乾燥工程を含んでもよい。
また、上記乾燥工程は膜形成工程の後、露光工程の前に行われることが好ましい。
乾燥工程における膜の乾燥温度は50~150℃であることが好ましく、70℃~130℃がより好ましく、90℃~110℃が更に好ましい。また、減圧により乾燥を行っても良い。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、2分~7分がより好ましい。
このような態様によれば、膜内で塩基が均一に近い状態で発生しやすく、例えば矩形性に優れた硬化物のパターンが得られると推測される。
上記塩基発生基には、特定樹脂に含まれる塩基を生じる性質を示す構造、及び、上述の塩基発生剤に含まれる塩基を生じる性質を示す構造の両方が含まれる。また、その他の化合物として塩基を生じる性質を示す構造を含む化合物が存在する場合、この塩基を生じる性質を示す構造も塩基発生基に含まれる。
硬化物の矩形性の観点からは、上記X/Yは、0.92<X/Y<1.08であることが好ましく、0.94<X/Y<1.06であることがより好ましい。
上記X/Yは、後述の実施例に記載された方法により測定することが可能である。
上記膜は、膜を選択的に露光する露光工程に供される。
すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を選択的に露光する露光工程を含む。
選択的に露光するとは、膜の一部を露光することを意味している。また、選択的に露光することにより、膜には露光された領域(露光部)と露光されていない領域(非露光部)が形成される。
露光量は、本発明の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50~10,000mJ/cm2が好ましく、200~8,000mJ/cm2がより好ましい。
また、露光の方式は特に限定されず、本発明の樹脂組成物からなる膜の少なくとも一部が露光される方式であればよいが、フォトマスクを使用した露光、レーザーダイレクトイメージング法による露光等が挙げられる。
上記膜は、露光後に加熱する工程(露光後加熱工程)に供されてもよい。
すなわち、本発明の硬化物の製造方法は、露光工程により露光された膜を加熱する露光後加熱工程を含んでもよい。
露光後加熱工程は、露光工程後、現像工程前に行うことができる。
露光後加熱工程における加熱温度は、50℃~140℃であることが好ましく、60℃~120℃であることがより好ましい。
露光後加熱工程における加熱時間は、30秒間~300分間が好ましく、1分間~10分間がより好ましい。
露光後加熱工程における昇温速度は、加熱開始時の温度から最高加熱温度まで1~12℃/分が好ましく、2~10℃/分がより好ましく、3~10℃/分が更に好ましい。
また、昇温速度は加熱途中で適宜変更してもよい。
露光後加熱工程における加熱手段としては、特に限定されず、公知のホットプレート、オーブン、赤外線ヒーター等を用いることができる。
また、加熱に際し、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことも好ましい。
露光後の上記膜は、現像液を用いて現像してパターンを形成する現像工程に供される。
すなわち、本発明の硬化物の製造方法は、露光工程により露光された膜を現像液を用いて現像してパターンを形成する現像工程を含む。現像を行うことにより、膜の露光部及び非露光部のうち一方が除去され、パターンが形成される。
ここで、膜の非露光部が現像工程により除去される現像をネガ型現像といい、膜の露光部が現像工程により除去される現像をポジ型現像という。
現像工程において用いられる現像液としては、アルカリ水溶液、又は、有機溶剤を含む現像液が挙げられる。
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。
現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、膜が形成された基材を現像液に浸漬する方法、基材上に形成された膜にノズルを用いて現像液を供給するパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。
現像液がアルカリ水溶液である場合、リンス液としては、例えば水を用いることができる。現像液が有機溶剤を含む現像液である場合、リンス液としては、例えば、現像液に含まれる溶剤とは異なる溶剤(例えば、水、現像液に含まれる有機溶剤とは異なる有機溶剤)を用いることができる。
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。
リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材上でのパドルによる供給、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段によりリンス液を連続供給する方法がある。
リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
すなわち、リンス工程は、リンス液を上記露光後の膜に対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。
このような態様によれば、現像による塩基発生基の減少が抑制されており、破断伸びに優れた硬化物が得られやすいと考えられる。
ここで、露光工程後、上記現像工程前の膜であって、現像工程後に上記パターンとして残存する膜とは、膜の現像後に残存する部位をいい、ネガ型現像であれば露光部が、ポジ型現像であれば未露光部がこれに該当する。
上記塩基発生基には、特定樹脂に含まれる塩基を生じる性質を示す構造、及び、上述の塩基発生剤に含まれる塩基を生じる性質を示す構造の両方が含まれる。また、その他の化合物として塩基を生じる性質を示す構造を含む化合物が存在する場合、この塩基を生じる性質を示す構造も塩基発生基に含まれる。
硬化物の破断伸びの観点からは、上記F/Eは、0.92以上であることが好ましく、0.94以上であることがより好ましい。F/Eの上限は特に限定されず、例えば、5.0以下とすることができる。例えば、現像液及びリンス液の少なくとも一方に塩基発生剤を含有させる、現像後又はリンス後に塩基発生剤を含む処理液にパターンを接触させる等により、現像工程後又はリンス工程後の塩基発生基の含有量を増加させることもできる。
上記F/Eは、後述の実施例に記載された方法により測定することが可能である。
現像工程により得られたパターン(リンス工程を行う場合は、リンス後のパターン)は、上記現像により得られたパターンを50℃以上250℃以下の温度で加熱する加熱工程に供される。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを加熱する加熱工程を含んでもよい。
また、本発明の硬化物の製造方法は、現像工程を行わずに他の方法で得られたパターン、又は、膜形成工程により得られた膜を加熱する加熱工程を含んでもよい。
加熱工程において、ポリイミド前駆体等の樹脂は環化してポリイミド等の樹脂となる。
また、特定樹脂、又は特定樹脂以外の架橋剤における未反応の架橋性基の架橋なども進行する。
加熱工程における加熱温度(最高加熱温度)としては、50~250℃が好ましく、150~350℃がより好ましく、150~250℃が更に好ましく、160~250℃が一層好ましく、160~230℃が特に好ましい。
加熱温度は、特定樹脂から塩基が生じる温度として適宜設定することができる。
加えて、急速加熱可能なオーブンの場合、加熱開始時の温度から最高加熱温度まで1~8℃/秒の昇温速度で行うことが好ましく、2~7℃/秒がより好ましく、3~6℃/秒が更に好ましい。
上記加熱温度の上限は、250℃以下であることが好ましく、240℃以下であることがより好ましく、230℃以下であることが更に好ましい。
更に、加熱後冷却してもよく、この場合の冷却速度としては、1~5℃/分であることが好ましい。
加熱工程における加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブン、赤外線オーブンなどが挙げられる。
現像工程により得られた(リンス工程を行う場合は、リンス後のパターン)は、上記加熱工程に上記加熱工程に加えて、現像工程後のパターンを露光する現像後露光工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを露光する現像後露光工程を含んでもよい。本発明の硬化物の製造方法は、加熱工程及び現像後露光工程を含んでもよいし、加熱工程及び現像後露光工程の一方のみを含んでもよい。
現像後露光工程においては、例えば、光塩基発生剤の感光によってポリイミド前駆体等の環化が進行する反応や、光酸発生剤の感光によって酸分解性基の脱離が進行する反応などを促進することができる。
現像後露光工程においては、現像工程において得られたパターンの少なくとも一部が露光されればよいが、上記パターンの全部が露光されることが好ましい。
現像後露光工程における露光量は、感光性化合物が感度を有する波長における露光エネルギー換算で、50~20,000mJ/cm2であることが好ましく、100~15,000mJ/cm2であることがより好ましい。
現像後露光工程は、例えば、上述の露光工程における光源を用いて行うことができ、ブロードバンド光を用いることが好ましい。
現像工程により得られたパターン(加熱工程及び現像後露光工程の少なくとも一方に供されたものが好ましい)は、パターン上に金属層を形成する金属層形成工程に供されてもよい。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターン(加熱工程及び現像後露光工程少なくとも一方に供されたものが好ましい)上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。
上記態様によれば、基材と接する側の付近と、基材と接する側とは反対の側の付近において膜シュリンクが同程度となるため、硬化物の矩形性が向上すると推測される。
閉環率とは、特定樹脂がポリイミド前駆体又はポリアミドイミド前駆体であればイミド化率、ポリベンゾオキサゾール前駆体であればオキサゾール化率をいう。
硬化物の矩形性の観点からは、上記A/Bは、0.92<A/B<1.08であることが好ましく、0.94<A/B<1.06であることがより好ましい。
上記A/Bは、後述の実施例に記載された方法により測定することが可能である。
上記態様によれば、基材と接する側の付近と、基材と接する側とは反対の側の付近において加熱の前後における膜シュリンクが同程度となるため、硬化物の矩形性が向上すると推測される。
硬化物の矩形性の観点からは、上記C/Dは、0.92<C/D<1.08であることが好ましく、0.94<C/D<1.06であることがより好ましい。
上記C/Dは、後述の実施例に記載された方法により測定することが可能である。
本発明の硬化物の製造方法、又は、本発明の硬化物の適用可能な分野としては、半導体デバイスの絶縁膜、再配線層用層間絶縁膜、ストレスバッファ膜などが挙げられる。そのほか、封止フィルム、基板材料(フレキシブルプリント基板のベースフィルムやカバーレイ、層間絶縁膜)、又は上記のような実装用途の絶縁膜をエッチングでパターン形成することなどが挙げられる。これらの用途については、例えば、サイエンス&テクノロジー(株)「ポリイミドの高機能化と応用技術」2008年4月、柿本雅明/監修、CMCテクニカルライブラリー「ポリイミド材料の基礎と開発」2011年11月発行、日本ポリイミド・芳香族系高分子研究会/編「最新ポリイミド 基礎と応用」エヌ・ティー・エス,2010年8月等を参照することができる。
本発明の積層体とは、本発明の硬化物からなる層を複数層有する構造体をいう。
本発明の積層体は、硬化物からなる層を2層以上含む積層体であり、3層以上積層した積層体としてもよい。
上記積層体に含まれる2層以上の上記硬化物からなる層のうち、少なくとも1つが本発明の硬化物からなる層であり、硬化物の収縮、又は、上記収縮に伴う硬化物の変形等を抑制する観点からは、上記積層体に含まれる全ての硬化物からなる層が本発明の硬化物からなる層であることも好ましい。
すなわち、本発明の積層体の製造方法は、複数回行われる硬化物の製造方法の間に、硬化物からなる層上に金属層を形成する金属層形成工程を更に含むことが好ましい。金属層形成工程の好ましい態様は上述の通りである。
上記積層体としては、例えば、第一の硬化物からなる層、金属層、第二の硬化物からなる層の3つの層がこの順に積層された層構造を少なくとも含む積層体が好ましいものとして挙げられる。
上記第一の硬化物からなる層及び上記第二の硬化物からなる層は、いずれも本発明の硬化物からなる層であることが好ましい。上記第一の硬化物からなる層の形成に用いられる本発明の樹脂組成物と、上記第二の硬化物からなる層の形成に用いられる本発明の樹脂組成物とは、組成が同一の組成物であってもよいし、組成が異なる組成物であってもよい。本発明の積層体における金属層は、再配線層などの金属配線として好ましく用いられる。
本発明の積層体の製造方法は、積層工程を含むことが好ましい。
積層工程とは、パターン(樹脂層)又は金属層の表面に、再度、(a)膜形成工程(層形成工程)、(b)露光工程、(c)現像工程、(d)加熱工程及び現像後露光工程の少なくとも一方を、この順に行うことを含む一連の工程である。ただし、(a)の膜形成工程および(d)加熱工程及び現像後露光工程の少なくとも一方を繰り返す態様であってもよい。また、(d)加熱工程及び現像後露光工程の少なくとも一方の後には(e)金属層形成工程を含んでもよい。積層工程には、更に、上記乾燥工程等を適宜含んでいてもよいことは言うまでもない。
例えば、樹脂層/金属層/樹脂層/金属層/樹脂層/金属層のように、樹脂層を2層以上20層以下とする構成が好ましく、2層以上9層以下とする構成が更に好ましい。
上記各層はそれぞれ、組成、形状、膜厚等が同一であってもよいし、異なっていてもよい。
本発明の積層体の製造方法は、上記金属層および樹脂組成物層の少なくとも一部を表面活性化処理する、表面活性化処理工程を含むことが好ましい。
表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記現像工程の後(好ましくは、加熱工程及び現像後露光工程の少なくとも一方の後)、樹脂組成物層に表面活性化処理工程を行ってから、金属層形成工程を行ってもよい。
表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、露光後の樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および露光後の樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる樹脂組成物層(膜)との密着性を向上させることができる。
また、表面活性化処理は、露光後の樹脂組成物層(樹脂層)の一部または全部についても行うことが好ましい。このように、樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や樹脂層との密着性を向上させることができる。特にネガ型現像を行う場合など、樹脂組成物層が硬化されている場合には、表面処理によるダメージを受けにくく、密着性が向上しやすい。
表面活性化処理としては、具体的には、各種原料ガス(酸素、水素、アルゴン、窒素、窒素/水素混合ガス、アルゴン/酸素混合ガスなど)のプラズマ処理、コロナ放電処理、CF4/O2、NF3/O2、SF6、NF3、NF3/O2によるエッチング処理、紫外線(UV)オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、500~200,000J/m2が好ましく、1000~100,000J/m2がより好ましく、10,000~50,000J/m2が最も好ましい。
本発明は、本発明の硬化物、又は、本発明の積層体を含む半導体デバイスも開示する。
また、本発明は、本発明の硬化物の製造方法、又は、本発明の積層体の製造方法を含む半導体デバイスの製造方法も開示する。本発明の樹脂組成物を再配線層用層間絶縁膜の形成に用いた半導体デバイスの具体例としては、特開2016-027357号公報の段落0213~0218の記載及び図1の記載を参酌でき、これらの内容は本明細書に組み込まれる。
本発明の環化樹脂の前駆体は、下記式(2)で表される繰返し単位、式(3)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よりなる群から選ばれる、少なくとも1種の繰返し単位を含む。
また、式(1-1)の好ましい態様は、上述の特定樹脂における式(1-1)の好ましい態様と同様である。
また、式(2)、式(3)及び式(PAI-2)の好ましい態様は、構造中に上述の式(1-1)で表される構造を含む以外は、特定樹脂における式(2)、式(3)及び式(PAI-2)の好ましい態様と同様である。
〔合成例1:環化樹脂の前駆体(樹脂1)の合成〕
4,4’-オキシジフタル酸二無水物(ODPA)46.96gをセパラブルフラスコに入れ、37.71gの2-ヒドロキシエチルメタクリレート(HEMA)、3.80gの(3-(2,5-ジヒドロキシフェニル)-1-(ピぺリジン-1-イル)プロパン-1-オン)、136.83gのテトラヒドロフランを入れて室温(25℃)下で撹拌し、撹拌しながらピリジン24.66gを加えて反応混合物を得た。反応による発熱の終了後に室温まで放冷し、16時間放置した。
次に、氷冷下において、ジシクロヘキシルカルボジイミド(DCC)62.46gをテトラヒドロフラン61.57gに溶解した溶液を撹拌しながら40分かけて反応混合物に加え、続いて4,4’-ジアミノジフェニルエーテル(DADPE)27.42gをテトラヒドロフラン119.73gに懸濁したものを撹拌しながら60分かけて加えた。更に室温で2時間撹拌した後、エチルアルコール7.17gを加えて1時間撹拌し、次に、テトラヒドロフラン136.83gを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。
得られた反応液を716.21gのエチルアルコールに加えて粗ポリマーから成る沈殿物を生成した。生成した粗ポリマーを濾別し、テトラヒドロフラン403.49gに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を8470.26gの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾別した後、真空乾燥して粉末状の樹脂1を80.3g得た。樹脂1の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。樹脂1は、下記式(P-1)で表される構造であって、Rが式(R-1)で表される構造である繰返し単位を含むと推測される。式(R-1)におけるmol%の記載は、各構造の含有モル比を表す。また、式における*は、Rが結合する酸素原子との結合部位を表す。
21.2gの4,4’-オキシジフタル酸無水物と、17.0gの2-ヒドロキシエチルメタクリレートと、1.7gの(3-(2,5-ジヒドロキシフェニル)-1-(ピぺリジン-1-イル)プロパン-1-オン)と、23.9gのピリジンと、250mLのジグリム(ダイグライム、ジエチレングリコールジメチルエーテル)とを混合し、60℃の温度で4時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートとのジエステルを合成した。次いで、反応混合物を-10℃に冷却し、温度を-10±5℃に保ちながら、17.0gの塩化チオニルを60分かけて加えた。50mLのN-メチルピロリドンで希釈した後、100mLのN-メチルピロリドンに12.6gの4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、-10±5℃で60分かけて反応混合物に滴下して、混合物を室温で2時間撹拌した。その後,エタノール(末端封止剤)10.0gを添加して室温で1時間撹拌した。
次いで、6000gの水に加えてポリイミド前駆体を沈殿させ、沈殿物(水-ポリイミド前駆体混合物)を15分間撹拌した。撹拌後の沈殿物(ポリイミド前駆体の固体)をろ取し、テトラヒドロフラン500gに溶解させた。得られた溶液に6000gの水(貧溶媒)を加えてポリイミド前駆体を沈殿させ、沈殿物(水-ポリイミド前駆体混合物)を15分間撹拌した。撹拌後の沈殿物(ポリイミド前駆体の固体)を再びろ過して減圧下で、45℃で3日間乾燥した。
乾燥後の粉体46.6gをテトラヒドロフラン419.6gに溶解させた後に、2.3gのトリエチルアミンを添加して室温で35分間撹拌した。その後、エタノール3000gに添加して、沈殿物をろ取した。得られた沈殿物をテトラヒドロフラン281.8gに溶解した。そこに水17.1gとイオン交換樹脂UP6040(AmberTec社製)46.6gを添加して、4時間撹拌した。その後、イオン交換樹脂をろ過で取り除き、得られたポリマー溶液をヘプタン4500gと酢酸エチル500gの混合溶液に加えて沈殿物を得た。沈殿物をろ取し、減圧下45℃で24時間乾燥させることで、樹脂2を45.1g得た。
樹脂2の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。また、4,4’-ジアミノジフェニルエーテルの当量を適宜調整することにより、Mwが4,500である樹脂2、Mwが7,500である樹脂2、Mwが10,000である樹脂2、Mwが30,000である樹脂2、Mwが50,000である樹脂2、Mwが100,000である樹脂2についてもそれぞれ合成した。樹脂2は、下記式(P-1)で表される構造であって、Rが式(R-1)で表される構造である繰返し単位を含むと推測される。式(R-1)におけるmol%の記載は、各構造の含有モル比を表す。また、式における*は、Rが結合する酸素原子との結合部位を表す。
使用する化合物を適宜変更した以外は、合成例2と同様の方法により樹脂3~樹脂20を合成した。各樹脂の合成において使用した原料は、後述の表に記載した。
樹脂3~20のMwはいずれも20,000であった。
樹脂3~樹脂23は、それぞれ、式(P-1)で表される構造であって、Rが式(R-2)~式(R-22)で表される構造である繰返し単位を含むと推測される。各式におけるmol%の記載は、各構造の含有モル比を表す。樹脂1~23における式(P-1)におけるRの構造を表1に示す。
4,4’-オキシジフタル酸二無水物(ODPA)23.48gとビスフタル酸二無水物 (BPDA)22.27g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)39.69gとテトラヒドロフラン136.83gを入れて室温(25℃)下で撹拌し、撹拌しながらピリジン24.66gを加えて反応混合物を得た。反応による発熱の終了後に室温まで放冷し、16時間放置した。
次に、氷冷下において、ジシクロヘキシルカルボジイミド(DCC)62.46gをテトラヒドロフラン61.57gに溶解した溶液を撹拌しながら40分かけて反応混合物に加え、続いて4,4’-ジアミノジフェニルエーテル(DADPE)27.42gをテトラヒドロフラン119.73gに懸濁したものを撹拌しながら60分かけて加えた。更に室温で2時間撹拌した後、エチルアルコール7.17gを加えて1時間撹拌し、次に、テトラヒドロフラン136.83gを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。
得られた反応液を716.21gのエチルアルコールに加えて粗ポリマーから成る沈殿物を生成した。生成した粗ポリマーを濾別し、テトラヒドロフラン403.49gに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を8470.26gの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾別した後、真空乾燥して粉末状の比較樹脂1を80.3g得た。比較樹脂1の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。比較樹脂1の構造は、下記式(CP-1)で表される構造であると推測される。
各実施例において、それぞれ、下記表に記載の成分を混合し、各樹脂組成物を得た。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、表に記載の各成分の含有量(配合量)は、表の各欄の「質量部」の欄に記載の量(質量部)とした。
得られた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用いて加圧ろ過した。
また、表中、「-」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。
・樹脂1~樹脂35:上記合成例により得られた樹脂1~樹脂35
・比較樹脂1:上記合成例により得られた比較樹脂1
・NMP:N-メチル-2-ピロリドン
・EL:乳酸エチル
・DMSO:ジメチルスルホキシド
・GBL:γ-ブチロラクトン
〔F/Eの測定〕
各実施例及び各比較例において調製した樹脂組成物又は比較用組成物を、それぞれ、スピンコート法でシリコンウエハ上に適用して樹脂層を形成した。
得られた樹脂層が形成されたシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に均一な厚さの樹脂組成物層を得た。膜厚は、表中の「膜厚(μm)」の欄の記載(硬化後の膜厚)が「20」である例については「約26μm」、「10」である例については「約13μm」、「30」と記載された例については「約40μm」とした。
上記樹脂組成物層の一部に関して、表中の現像条件の欄に「ネガ」と記載されている例においては、シリコンウエハ上の樹脂組成物層の全面を、500mJ/cm2の露光エネルギーで露光した。露光波長は表中の「露光波長(nm)」に記載した。表中の現像条件の欄に「ポジ」と記載されている例においては、露光を行わなかった。上記露光後、表に記載の現像液に上記樹脂組成物層を浸漬することで現像後の膜(パターン)を得た。
現像前後の膜それぞれについて、重DMSOを用いることで1H-NMR測定およびHPLC測定を行い、現像前後の膜に残存する塩基発生成分(塩基発生基のモル量)を定量した。
現像前の膜中に存在する塩基発生基のモル量Eと、現像後の膜中に存在する塩基発生基のモル量Fの比F/Eを算出し、表の「F/E」の欄に記載した。
表の「膜厚(μm)」の欄に記載の膜厚を持つ膜を形成した後に,ガスクラスターイオンビーム(GCIB)法により膜の厚み方向に掘削した。掘削部位に関してFT-IR測定を実施することで,各部位における塩基発生基の濃度を算出した。
具体的には、膜の厚み方向の上部50%における塩基発生基の濃度Xと下部50%における塩基発生基の濃度Yの比X/Yを算出し、表の「X/Y」の欄に記載した。
後述の破断伸びの評価と同様の方法により硬化後の樹脂組成物層(硬化物)を作製した。硬化物が形成されたシリコンウエハを4.9質量%フッ化水素酸水溶液に浸漬し、シリコンウエハから硬化物を剥離した。得られた剥離膜の表面側(シリコンウエハとは反対の側)とシリコンウエハと接していた側のそれぞれについてFT-IR測定を実施することで、各面の閉環率を算出した。
FT-IR測定は下記のように行った。
樹脂として樹脂1~33を用いた場合には、FT-IRにより測定される赤外吸収スペクトルにおける、イミド構造由来の吸収ピークである1377cm-1付近のピーク強度P1を、上記表面側と、シリコンウエハと接していた側についてそれぞれ測定した。次に、硬化物を350℃、1時間で熱処理した後、再度、FT-IR測定を行い、上記表面側と、シリコンウエハと接していた側についてそれぞれ1377cm-1付近のピーク強度P2を求めた。
得られたピーク強度P1、P2を用い、下記式に基づいて、ポリイミドのイミド化率(閉環率)を求めた。
イミド化率(%)=(ピーク強度P1/ピーク強度P2)×100
樹脂として樹脂34、35を用いた場合には、アミド構造に由来する吸収ピークである1650cm-1付近のピーク強度Q1を求め、次に、1490cm-1付近に見られる芳香環の吸収強度で規格化した。そのポリベンゾオキサゾールを350℃で1時間熱処理した後、再度、赤外吸収スペクトルを測定し、1650cm-1付近のピーク強度Q2を求め、1490cm-1付近に見られる芳香環の吸収強度で規格化した。得られたピーク強度Q1、Q2の規格値を用い、下記式に基づいて、ポリベンゾオキサゾールのオキサゾール化率(閉環率)を求めた。
オキサゾール化率(%)=(ピーク強度Q1の規格値/ピーク強度Q2の規格値)×100
具体的には、硬化物のシリコンウエハと接する側とは反対の側の表面における閉環率Aとシリコンウエハと接する側の表面における閉環率Bの比A/Bを算出し、表の「A/B」の欄に記載した。
膜厚を変更し、加熱時間を180分間とした以外は、後述のパターン矩形性の評価と同様の方法により、膜厚20μm、ピッチ10μmの1:1ラインアンドスペースパターン状の硬化膜を得た。加熱工程前後(キュアの前後)のラインアンドスペースパターンそれぞれについて断面SEMを測定することにより、ラインパターン上端における幅収縮率と下端における幅収縮率を算出した。
具体的には、ラインパターンの上端における幅収縮率Cと下端における幅収縮率Dの比C/Dを算出し、表の「C/D」の欄に記載した。
各実施例及び各比較例において調製した樹脂組成物又は比較用組成物を、それぞれ、スピンコート法でシリコンウエハ上に適用して樹脂層を形成した。
得られた樹脂層が形成されたシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に表中の「膜厚(μm)」の欄の記載(硬化後の膜厚)が「20」である例については「約26μm」、「10」である例については「約13μm」、「30」と記載された例については「約40μm」とした。均一な厚さの樹脂組成物層を得た。
表中の現像条件の欄に「ネガ」と記載されている例においては、シリコンウエハ上の樹脂組成物層の全面を、500mJ/cm2の露光エネルギーで露光した。露光波長は表中の「露光波長(nm)」に記載した。表中の現像条件の欄に「ポジ」と記載されている例においては、露光を行わなかった。
露光条件の欄に「M」と記載された例においては、光源としてステッパーを用いて露光した。
露光条件の欄に「LDI」と記載された例においては、光源として、ダイレクト露光装置(アドテック DE-6UH III)を用いて露光した。
「キュア温度(℃)」の欄に数値が記載された例においては、ホットプレートを使用して、上記露光後の樹脂組成物層を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表の「キュア温度(℃)」の欄に記載の温度に達した後、上記温度を表の「キュア時間(min)」の間維持した。
「キュア温度(℃)」の欄に「IR」と記載された例においては、赤外線ランプ加熱装置(アドバンス理工社製、RTP-6)を用いて、各実施例において得られた樹脂膜を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、上記温度を180分間維持した。
硬化後の樹脂組成物層(硬化物)を4.9質量%フッ化水素酸水溶液に浸漬し、シリコンウエハから硬化物を剥離した。剥離した硬化物を、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。得られた試験片の長手方向の伸び率を、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、25℃、65%RH(相対湿度)の環境下にて、JIS-K6251に準拠して測定した。測定は各5回ずつ実施し、5回の測定における試験片が破断した時の伸び率(破断伸び率)の算術平均値を指標値として用いた。
評価は下記評価基準に従って行い、評価結果は表の「破断伸び」の欄に記載した。指標値が大きいほど、硬化物は膜強度に優れるといえる。
-評価基準-
A:上記指標値が65%以上であった。
B:上記指標値が60%以上65%未満であった。
C:上記指標値が55%以上60%未満であった。
D:上記指標値が55%未満であった。
各実施例及び比較例において、それぞれ、各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層状に適用(塗布)して、樹脂組成物膜を形成した。
各実施例及び比較例において、得られた樹脂組成物膜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樹脂組成物膜を形成した。
シリコンウェハ上の樹脂組成物膜を、表の「露光波長(μm)」の欄に記載の露光波長を用いて、500mJ/cm2の露光エネルギーで露光した。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、線幅が表中の「パターンサイズ(μm)」の欄に記載の線幅であるバイナリマスク)を介して行った。
上記露光後、表の「現像条件」の欄に「ポジ」と記載された例においては、2.5質量%テトラメチルアンモニウムヒドロキシド水溶液を用いて60秒間現像し、純水で20秒間リンスして、露光後の樹脂組成物膜のラインアンドスペースパターンを得た。表の「現像条件」の欄に「ネガ」と記載された例においては、シクロペンタノンを用いて60秒間現像し、プロピレングリコールモノメチルエーテルアセテート(PGMEA)で20秒間リンスして、樹脂組成物膜のラインアンドスペースパターンを得た。
次に指定されたキュア(硬化)条件でキュアを行った。具体的には、「キュア温度(℃)」の欄に数値が記載された例においては、ホットプレートを使用して、上記露光後の樹脂組成物層を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表の「キュア温度(℃)」の欄に記載の温度に達した後、上記温度を表の「キュア時間(min)」に記載の時間において維持した。また、表の「キュア温度(℃)」の欄に「IR」と記載された例では,赤外線ランプ加熱装置(アドバンス理工社製、RTP-6)を用いて各実施例において得られた現像後の樹脂組成物膜を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、上記温度を180分間維持した。
得られた硬化膜が形成されたシリコンウェハについて、硬化膜のラインアンドスペースパターンに対して垂直になるようにシリコンウェハをカットし、パターン断面を露出させた。光学顕微鏡を用いて、倍率200倍で、上記ラインアンドスペースパターンのパターン断面を観察し、パターンの断面形状の評価を行った。
具体的には、各実施例及び比較例において、それぞれ、シリコンウェハの表面(基板表面)と硬化膜の側面とのなすテーパ角を測定し、下記評価基準に従って評価した。評価結果は表の「パターン矩形性」の欄に記載した。テーパ角が90°を超えず、かつ、パターンの断面形状がくびれた形状ではなく、テーパ角が90°に近いほど、パターン形状に優れるといえる。
-評価基準-
A:テーパ角が85°以上90°以下であった。
B:テーパ角が80°以上85°未満であった。
C:テーパ角が75°以上80°未満であった。
D:テーパ角が75°未満であるか、パターンの断面形状が90°を超えるテーパ角をなす逆テーパ形状であるか、又は、パターンの断面形状がくびれた形状であった。
各実施例及び比較例において、それぞれ、各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層状に適用(塗布)して、樹脂組成物膜を形成した。
各実施例及び比較例において、得られた樹脂組成物膜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樹脂組成物膜を形成した。
シリコンウェハ上の樹脂組成物膜を、表の「露光波長(nm)」の欄に記載の露光波長を用いて、500mJ/cm2の露光エネルギーで露光した。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、線幅が表「パターンサイズ(μm)」の欄に記載の線幅であるバイナリマスク)を介して行った。
上記露光後、表の「現像条件」の欄に「ポジ」と記載された例においては、2.5質量%テトラメチルアンモニウムヒドロキシド水溶液を用いて60秒間現像し、純水で20秒間リンスして、露光後の樹脂組成物膜のラインアンドスペースパターンを得た。表の「現像条件」の欄に「ネガ」と記載された例においては、シクロペンタノンを用いて60秒間現像し、プロピレングリコールモノメチルエーテルアセテート(PGMEA)で20秒間リンスして、樹脂組成物膜のラインアンドスペースパターンを得た。
得られたラインアンドスペースパターンについて、測長走査型電子顕微鏡(SEM(株)日立製作所S-9380II)にてパターン上部から観察し、ラインパターンの長手方向のエッジ2000μmの範囲について線幅を測定し、その線幅の測定ばらつきについて標準偏差σを求め、3σを算出した。値が小さいほど良好な性能であることを示す。評価結果は表の「現像後パターンラフネス」の欄に記載した。
-評価基準-
A:3σが50nm未満であった。
B:3σが50nm以上75nm未満であった。
C:3σが75nm以上100nm未満であった。
D:3σが100nm以上であった。
比較例1における比較用組成物は、特定樹脂を含まない。このような態様においては、得られる硬化物におけるパターンの矩形性に劣ることがわかる。
実施例1において使用した樹脂組成物を、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の感光膜を形成した後、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。露光後、100℃で4分間加熱した。上記加熱後、シクロヘキサノンで2分間現像し、PGMEAで30秒間リンスし、層のパターンを得た。
次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、230℃で120分間維持して、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。
Claims (19)
- 環化樹脂の前駆体を含み
前記環化樹脂の前駆体は、250℃に加熱した場合に塩基が発生する環化樹脂の前駆体である
樹脂組成物。 - 前記加熱時に、前記塩基が前記環化樹脂の前駆体から遊離する、請求項1に記載の樹脂組成物。
- 前記環化樹脂の前駆体に含まれる塩基を発生する性質を示す構造が、非イオン性の構造である、請求項1又は2に記載の樹脂組成物。
- 前記環化樹脂の前駆体に含まれる塩基を発生する性質を示す構造が、アミド結合を含む、請求項1~3のいずれか1項に記載の樹脂組成物。
- 前記アミド結合が、カルボニル基側で前記環化樹脂の前駆体の主鎖と結合する、請求項4に記載の樹脂組成物。
- 光重合開始剤を更に含む、請求項1~6のいずれか1項に記載の樹脂組成物。
- 重合性化合物を更に含む、請求項1~7のいずれか1項に記載の樹脂組成物。
- 塩基発生剤を更に含む、請求項1~8のいずれか1項に記載の樹脂組成物。
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~9のいずれか1項に記載の樹脂組成物。
- 請求項1~10のいずれか1項に記載の樹脂組成物を硬化してなる硬化物。
- 請求項11に記載の硬化物からなる層を2層以上含み、前記硬化物からなる層同士のいずれかの間に金属層を含む積層体。
- 請求項11に記載の硬化物又は請求項12に記載の積層体を含む、半導体デバイス。
- 環化樹脂の前駆体を含む樹脂組成物を基材上に適用して膜を形成する膜形成工程、
前記膜を選択的に露光する工程、
前記膜を現像液を用いて現像してパターンを形成する現像工程、及び、
前記パターンを50℃以上250℃以下の温度で加熱する加熱工程を含み、
前記環化樹脂の前駆体は、前記加熱工程において塩基を生じる化合物である
硬化物の製造方法。 - 露光工程後、現像工程前の膜であって、現像工程後に前記パターンとして残存する膜中に存在する塩基発生基のモル数Eと、前記現像工程後の前記パターン中に存在する塩基発生基のモル数Fの比F/Eが、0.9を超える、請求項14に記載の硬化物の製造方法。
- 前記膜形成工程において形成された前記膜において、膜の厚み方向の上部50%における塩基発生基の濃度Xと下部50%における塩基発生基の濃度Yの比X/Yが、0.90<X/Y<1.10である、請求項14又は15に記載の硬化物の製造方法。
- 得られる硬化物の前記基材と接する側とは反対の側の表面における閉環率Aと前記基材と接する側の表面における閉環率Bの比A/Bが、0.90<A/B<1.10である、請求項14~16のいずれか1項に記載の硬化物の製造方法。
- 現像工程において、膜厚20μm、ピッチ10μmの1:1ラインアンドスペースパターンを形成し、加熱工程において230℃で180分間加熱した場合に、ラインパターンの上端における幅収縮率Cと下端における幅収縮率Dの比C/Dが、0.90<C/D<1.10である、請求項14~17のいずれか1項に記載の硬化物の製造方法。
- 下記式(2)で表される繰返し単位、式(3)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よりなる群から選ばれる、少なくとも1種の繰返し単位を含む、環化樹脂の前駆体。
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JPH04291235A (ja) * | 1991-03-19 | 1992-10-15 | Fuji Photo Film Co Ltd | 液晶表示素子 |
JP2006028098A (ja) * | 2004-07-16 | 2006-02-02 | Chisso Corp | フェニレンジアミン、それを用いて形成される配向膜、および該配向膜を含む液晶表示素子 |
WO2017038598A1 (ja) * | 2015-08-28 | 2017-03-09 | 富士フイルム株式会社 | 硬化膜の製造方法、再配線層用層間絶縁膜の製造方法、および、半導体デバイスの製造方法 |
JP2019185031A (ja) * | 2018-04-16 | 2019-10-24 | 旭化成株式会社 | ネガ型感光性樹脂組成物及び硬化レリーフパターンの製造方法 |
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JPH04291235A (ja) * | 1991-03-19 | 1992-10-15 | Fuji Photo Film Co Ltd | 液晶表示素子 |
JP2006028098A (ja) * | 2004-07-16 | 2006-02-02 | Chisso Corp | フェニレンジアミン、それを用いて形成される配向膜、および該配向膜を含む液晶表示素子 |
WO2017038598A1 (ja) * | 2015-08-28 | 2017-03-09 | 富士フイルム株式会社 | 硬化膜の製造方法、再配線層用層間絶縁膜の製造方法、および、半導体デバイスの製造方法 |
JP2019185031A (ja) * | 2018-04-16 | 2019-10-24 | 旭化成株式会社 | ネガ型感光性樹脂組成物及び硬化レリーフパターンの製造方法 |
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