WO2023008049A1 - 硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、樹脂組成物、硬化物、積層体、及び、半導体デバイス - Google Patents
硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、樹脂組成物、硬化物、積層体、及び、半導体デバイス Download PDFInfo
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- XLRPYZSEQKXZAA-OCAPTIKFSA-N tropane Chemical compound C1CC[C@H]2CC[C@@H]1N2C XLRPYZSEQKXZAA-OCAPTIKFSA-N 0.000 description 1
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Classifications
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
Definitions
- the present invention relates to a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, a resin composition, a cured product, a laminate, and a semiconductor device.
- 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 at least one of a cyclized resin such as polyimide and 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.
- the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition to be applied. It can be said that it is excellent in sex.
- cyclized resins such as polyimide, from the viewpoint of such excellent manufacturing adaptability, industrial application and development of the above-mentioned resin compositions are increasingly expected.
- Patent Document 1 a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having a larger area than the semiconductor chip in a plan view are provided, and an interlayer insulating film of the rewiring layer is provided.
- a semiconductor device having a weight reduction rate of 5 to 95% by weight after being heated to 700° C. at 10° C./min in an air atmosphere is disclosed.
- the present invention is to provide a method for producing a cured product that provides a cured product having excellent adhesion to metals, and a method for producing a laminate and a method for producing a semiconductor device using the above method for producing a cured product. aim.
- the present invention provides a resin composition from which a cured product having excellent adhesion to metal can be obtained, a cured product obtained by curing the resin composition, a laminate and a semiconductor device containing the cured product. The purpose is to
- a film forming step of applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film, and A method for producing a cured product comprising a heating step of heating the film at a heating temperature of 180 ° C. or less, After the heating step, the film was heated from 25° C. to 260° C. at a rate of 10° C./min, maintained at 260° C. for 15 minutes, and heated from 260° C. to 300° C. at a rate of 10° C./min.
- the mass reduction rate represented by the following formula A is 15% or less
- a method for producing a cured product wherein the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the obtained cured product is 95% or more.
- Formula A: Mass reduction rate (%) ⁇ 1-(mass of film after heating at 300°C)/(mass of film at 25°C) ⁇ x 100 ⁇ 2>
- ⁇ 3> The method for producing a cured product according to ⁇ 1> or ⁇ 2>, wherein the mass reduction rate is 10% or less.
- ⁇ 4> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 3>, wherein the mass reduction rate is 5% or less.
- ⁇ 5> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 4>, wherein the cyclization rate is 98% or more.
- ⁇ 6> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 5>, wherein the film after the heating step is a polyimide film.
- ⁇ 7> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 6>, further comprising an exposure step of selectively exposing the film between the film forming step and the heating step. .
- ⁇ 8> The method for producing a cured product according to ⁇ 7>, further comprising, between the exposure step and the heating step, a developing step of developing the exposed film with a developer to form a pattern.
- ⁇ 9> The method for producing a cured product according to ⁇ 8>, wherein the developer contains an organic solvent.
- the developing step is a step of forming a negative pattern.
- ⁇ 11> The method for producing a cured product according to any one of ⁇ 8> to ⁇ 10>, wherein the developer contains a base.
- ⁇ 12> The cured product according to any one of ⁇ 8> to ⁇ 11>, including a treatment step of contacting the pattern with a treatment liquid containing a base between the development step and the heating step.
- Production method. ⁇ 13> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 12>, wherein the resin composition contains a photosensitizer. ⁇ 14> ⁇ 1> to ⁇ 13>, wherein the resin composition contains a solvent and the content of the precursor of the cyclized resin is 70% by mass or more relative to the total solid content of the resin composition.
- ⁇ 15> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 14>, wherein the resin composition contains a polymerizable compound having a boiling point of 270° C. or higher at 1 atmosphere.
- the polymerizable compound having a boiling point of 270°C or higher at 1 atm is a compound having three or more (meth)acrylate groups.
- ⁇ 17> Any of ⁇ 1> to ⁇ 16>, wherein the content of the component having a molecular weight of 1000 or less and being different from the solvent is 30% by mass or less with respect to the total solid content of the resin composition.
- the precursor of the cyclized resin contains a resin having at least one of repeating units represented by the following formula (1-1) and repeating units represented by the following formula (1-2):
- W 1 represents a divalent organic group
- X 1 represents a tetravalent organic group
- R 1 to R 3 each independently A group represented by the following formula (3-1) or a group represented by the formula (3-2)
- W 2 represents a divalent organic group
- X 2 represents a trivalent organic group.
- the resin is a repeating unit represented by the formula (1-1) in which at least one of R 1 and R 2 is a group represented by the formula (3-1), and a repeating unit represented by the formula (1- 2) in which R 3 is a group represented by formula (3-1).
- Z 1 and Z 2 each independently represent an organic group
- Z 1 and Z 2 may combine to form a ring structure
- a 2 represents an oxygen atom or —NH—
- R 113 represents a hydrogen atom or a monovalent organic group
- * represents a bonding site with another structure.
- a method for producing a semiconductor device comprising the method for producing a cured product according to any one of ⁇ 1> to ⁇ 18> or the method for producing a laminate according to ⁇ 19>.
- the cured product was heated from 25 ° C. to 260 ° C. at a rate of 10 ° C./min, maintained at 260 ° C. for 15 minutes, and heated from 260 ° C. to 300 ° C. at a rate of 10 ° C./min. Measure the mass loss rate.
- the mass reduction rate is calculated by the following formula A.
- Mass reduction rate (%) ⁇ 1-(mass of film after heating at 300°C)/(mass of film at 25°C) ⁇ ⁇ 100 ⁇ 22>
- ⁇ 23> Containing two or more layers of a cured product obtained by curing a resin composition containing a precursor of a cyclized resin, A laminate, wherein at least one of the layers comprising the cured product is a layer comprising the cured product according to ⁇ 22>.
- ⁇ 24> Including the cured product according to ⁇ 22> or the laminate according to ⁇ 23>, semiconductor device.
- cured material manufacturing method are provided.
- a resin composition from which a cured product having excellent adhesion to metal can be obtained, a cured product obtained by curing the resin composition, a laminate and a semiconductor device containing the cured product are provided. 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.
- alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
- 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.
- UV ray ultraviolet
- 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 specified. Combinations of preferred aspects are more preferred aspects herein.
- 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, and heating the film at a heating temperature of 180 ° C. or less.
- the film after the heating step is heated from 25 ° C. to 260 ° C. at a rate of 10 ° C./min, maintained at 260 ° C. for 15 minutes, and heated from 260 ° C. to 300 ° C.
- Mass reduction rate (%) ⁇ 1-(mass of film after heating at 300°C)/(mass of film at 25°C) ⁇ x 100
- the heating temperature in the heating step is 180° C. or less, and the film after the heating step is heated from 25° C. to 260° C. at a rate of 10° C./min.
- the temperature was raised from 260°C to 300°C at a rate of 10°C/min, the temperature was raised from 25°C to 260°C at a rate of 10°C/min, the temperature was maintained at 260°C for 15 minutes, and the temperature was maintained at 260°C to 300°C.
- the mass reduction rate when the temperature is raised at a rate of 10 ° C./min to 15% or less, and the cyclization rate of the cyclized resin obtained from the cyclized resin precursor in the resulting cured product is 95%. That's it.
- the mass reduction rate is 15% or less, it is presumed that the generation of outgassing is suppressed, and therefore the adhesion between the cured product and the metal is considered to be excellent.
- the cyclization rate is 95% or more, migration of metal ions from the metal layer to the cured product, which uses the uncyclized portion as a permeation path, is also considered to be suppressed.
- a cured product obtained by heating at a low temperature of 180 ° C. or less can obtain a cured product having excellent adhesion to metals. Conceivable.
- the cured product obtained by the production method of the cured product of the present invention has a high degree of cyclization, it is considered to be excellent in moisture resistance.
- the method for producing a cured product of the present invention includes a film forming step of applying a resin composition containing a cyclized resin precursor onto a substrate to form a film.
- the details of the resin composition will be described later.
- 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.
- Coating is preferable as a means of applying the resin composition onto the substrate.
- 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, ink jet method, etc.
- slit coating and spray coating are preferable for rectangular substrates.
- method, inkjet method, and the like are preferred.
- spin coating 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 above application method, onto a base material can also 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 suitably 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 process may also be employed in which the substrate is coated with various solvents before the resin composition is applied 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 method for producing a cured product of the present invention includes a heating step of heating the film at a heating temperature of 180° C. or less.
- the film in the heating step may be a film (pattern) after development that has undergone an exposure step and a development step, which will be described later, or a film that has undergone an exposure step, which will be described later, but has not undergone a development step.
- it may be a film formed by the above-described film forming step (and, if necessary, the above-described drying step) without undergoing other steps.
- the temperature of the film is preferably 180° C. or lower in all steps including the heating step.
- a resin such as a polyimide precursor is cyclized into a resin such as polyimide.
- cross-linking of unreacted cross-linkable groups in the specific resin described later or in a cross-linking agent other than the specific resin also progresses.
- the heating temperature (maximum heating temperature) in the heating step is preferably 20°C to 180°C, more preferably 150°C to 180°C, and even more preferably 160°C to 180°C.
- the film after the heating step is preferably a polyimide film.
- the resin contained in the film after the heating step is a resin having an imide ring structure in the repeating unit.
- the heating step is preferably a step of promoting the cyclization reaction of the precursor of the cyclized resin in the film by heating. It is more preferable that the step promotes the cyclization reaction of the precursor of the cyclized resin in the film by the action of the permeated base, the base permeated from the rinsing liquid, or the like. That is, before and after the heating step, it is preferable that the cyclization rate of the film after the heating step (that is, the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin) increases.
- the cyclization rate (%) of the film before the heating process is cyclization rate A
- the cyclization rate (%) of the film after the heating process is cyclization rate B
- the difference in cyclization rate between the two is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
- the upper limit of the cyclization rate is not particularly limited, and may be 100%.
- Difference in cyclization rate cyclization rate B - cyclization rate A A method for measuring the cyclization rate of the membrane will be described later.
- Heating in the heating step is preferably carried out at a temperature rising rate of 0.1 to 30° C./min from the temperature at the start of heating to the maximum heating temperature.
- the rate of temperature increase is more preferably 0.5 to 20°C/min, still more preferably 2 to 10°C/min.
- the temperature is preferably increased from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 30°C/sec, more preferably 2 to 20°C/sec, and 3 to 10°C/sec. °C/sec is more preferred.
- 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, 30 to 200° C. higher than the boiling point of the solvent contained in the resin composition. It is preferable to raise the temperature from a low temperature.
- the heating time (heating time at the maximum heating temperature) is preferably 30 minutes to 5 hours, more preferably 1 hour to 3 hours.
- the temperature fluctuation width when maintaining the maximum heating temperature is preferably 0.1 ° C. to 20 ° C., and 0.1 to 10 ° C. is more preferred, and 0.1°C to 3°C is more preferred.
- the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferably above 120°C, most preferably above 150°C. The upper limit of the heating temperature is 180°C or less.
- 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 180°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.
- the heating in the heating step may be performed under normal pressure or under reduced pressure.
- the pressure reduction may be completed before the start of heating, the pressure reduction may be completed during the temperature rise from the start of heating, or the pressure reduction may be completed after the maximum heating temperature is reached.
- the timing of completion of decompression is not particularly limited. Completion of pressure reduction means that the pressure becomes 20 mmHg (volume ratio) or less.
- the above pressure can be measured with a differential pressure gauge.
- the membrane is under reduced pressure during the entire time period during which the maximum heating temperature is maintained.
- the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, an infrared oven and the like.
- the film before the heating step may be subjected to an exposure step for selectively exposing the film.
- the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step between the film forming step and the heating 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 can be cured. For example, it is preferably 50 to 10,000 mJ/cm 2 and more preferably 200 to 8,000 mJ/cm 2 in terms of exposure energy at a wavelength of 365 nm. .
- 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 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 is exposed. Examples thereof include exposure using a photomask and exposure by a laser direct imaging method.
- 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. Before and after the post-exposure heating step, it is also preferred that the cyclization rate of the film after the heating step (that is, the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin) does not substantially increase. Specifically, the above-described difference in cyclization rate is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The upper limit of the cyclization rate is not particularly limited, and may be 0%.
- the difference in cyclization rate is preferably 30% or less, more preferably 20% or less, and 10% or less. More preferred.
- the upper limit of the cyclization rate is not particularly limited, and may be 0%.
- 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 1 to 12° C./min, more preferably 2 to 10° C./min, still more preferably 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. Moreover, it is also preferable to carry out the heating in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium or argon.
- the film after exposure may be subjected to a development step in which the film is developed using a developer to form a pattern.
- the method for producing a cured product of the present invention may include 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.
- the development in which the non-exposed portion of the film is removed by the development process is called negative development, and the formed pattern is called negative pattern.
- development in which the exposed portion of the film is removed by the development process is called positive development, and the formed pattern is called positive pattern.
- the developing step is preferably a step of forming a negative pattern.
- Examples of the developer used in the developing step include an aqueous alkaline solution and a developer containing an organic solvent, and the developer containing an organic solvent is preferable.
- 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 alkyloxyacetate (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. Further, when the developer contains an organic solvent, the content of water relative to the total weight of the developer is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less. is more preferable, and 0.1% by mass or less is particularly preferable. The content of water is not particularly limited, and may be 0% by mass.
- the developer contains at least one compound selected from the group consisting of bases and base generators.
- the base or base generator in the developer penetrates into the film, and in the subsequent heating step, the base or the base generated from the base generator acts to form a precursor of the cyclized resin. It is thought that the cyclization of is promoted.
- the developer preferably contains a base from the viewpoint of long-term adhesion between the metal and the cured product.
- the developer is preferably a developer containing an organic solvent.
- bases are organic bases from the viewpoint of reliability when remaining in the cured product (adhesion to the substrate when the cured product is further heated).
- a base having an amino group is preferable, and primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. are preferable.
- secondary amines and tertiary amines are preferred, secondary amines or tertiary amines are more preferred, and tertiary amines are most preferred.
- the base is preferably one that does not easily remain in the resulting cured product. It is preferable that the remaining amount is difficult to decrease before.
- the boiling point of the base is preferably 30°C to 350°C, more preferably 80°C to 270°C, even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
- the boiling point of the base is preferably higher than the boiling point of the organic solvent contained in the developer minus 20° C., and more preferably higher than the boiling point of the organic solvent contained in the developer.
- the base used preferably has a boiling point of 80° C. or higher, more preferably 100° C. or higher.
- the pKa of the conjugate acid of the base in DMSO is preferably 1 or more, more preferably 3 or more. Although the upper limit of the pKa is not particularly limited, it is preferably 20 or less. When the conjugate acid of the above base has multiple pKa's in DMSO, at least one of them is preferably within the above range.
- the above pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, Determination of Organic Structures by Physical Methods (Author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; Compilation: Braude, E.
- the base contained in the developer include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, dimethylcyclohexylamine, aniline, N-methyl Aniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo [2.2.2] octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine
- the content of the base relative to the total weight of the developer is preferably 0.1 to 100% by weight, more preferably 0.3 to 30% by weight, and 0.5 to 20% by weight. % is more preferred.
- the content of the base is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass.
- a base may be used individually by 1 type, and may use 2 or more types together. When two or more bases are used in the developer, the total content thereof is preferably within the above range.
- Base generator The developer may contain a base generator.
- the base generator include photobase generators and thermal base generators, with thermal base generators being preferred.
- the photobase generator or thermal base generator for example, the base generators described below as components contained in the resin composition can be used without particular limitation.
- the content of the base generator with respect to the total weight of the developer is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass. , more preferably 0.08 to 5% by mass.
- the base generator may be used singly or in combination of two or more. When two or more base generators are used in the developer, the total content thereof is preferably within the above range.
- 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 adopted.
- 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 is brought into contact with a processing solution containing at least one compound selected from the group consisting of bases and base generators between the developing step and the heating step. It is preferable to include a step, and it is more preferable to include, between the developing step and the heating step, a processing step of bringing the pattern into contact with a processing liquid containing a base. According to this aspect, it is considered that at least one compound selected from the group consisting of bases and base generators contained in the processing liquid permeates the pattern after development.
- the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin after the heating step increases, and even when heated at a low temperature of 180 ° C. or less, the adhesion between the metal and the cured product is improved. expected to improve.
- the treatment step is a rinse step of washing the pattern with the treatment liquid.
- the treatment liquid is preferably a rinse liquid.
- the treatment liquid is a rinse liquid
- the treatment step is a rinse step of washing the pattern with the rinse liquid. That is, the treatment step is preferably a rinse step of washing the pattern (pattern obtained by the development step) with a rinse solution containing at least one compound selected from the group consisting of bases and base generators. .
- the treatment process may be performed, for example, after "another rinsing process" to be described later.
- the water content relative to the total mass of the treatment liquid is preferably 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass or less. is more preferable, and 2% by mass or less is particularly preferable.
- the lower limit of the water content is not particularly limited, and may be 0% by mass.
- a solvent contained in the developer and a solvent different from the solvent contained in the developer for example, an organic solvent different from the organic solvent contained in the developer
- a solvent containing at least one compound selected from the group consisting of can be used.
- the boiling point of the base contained in the treatment liquid at normal pressure is preferably 300°C or lower, more preferably 250°C or lower, and 180°C or lower. is more preferred.
- the lower limit of the boiling point is not particularly limited, but when the treatment liquid contains an organic solvent, the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent (the lowest boiling point if multiple organic solvents are contained) and more preferably higher than the boiling point of the organic solvent contained in the treatment liquid.
- the base used preferably has a boiling point of 80° C. or higher, more preferably 100° C. or higher.
- Other preferred embodiments of the base contained in the processing liquid are the same as those of the base contained in the developing liquid described above.
- the content of the base relative to the total weight of the treatment liquid is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and 0.5% by mass. More preferably, it is up to 20% by mass. Also, when the base is not liquid at 10 to 30° C., the content of the base is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass.
- One type of base may be used alone, or two or more types may be used in combination. When two or more types of bases are used in combination in the treatment liquid, the total content thereof is preferably within the above range.
- the treatment liquid may contain a base generator.
- the base generator include photobase generators and thermal base generators, with thermal base generators being preferred.
- the photobase generator or thermal base generator for example, the photobase generator or thermal base generator described below as a component contained in the resin composition can be used without particular limitation.
- the content of the base generator relative to the total weight of the treatment liquid is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass. , more preferably 0.08 to 5% by mass.
- the base generator may be used singly or in combination of two or more. When two or more kinds of base generators are used in combination in the treatment liquid, the total content thereof is preferably within the above range.
- Organic solvents contained in the treatment liquid include esters 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., methyl 3-methoxypropionate , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
- 2-alkyloxypropionate alkyl esters e.g.
- methyl 2-alkyloxypropionate, 2-alkyloxypropionate ethyl acetate, propyl 2-alkyloxypropionate, etc. e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
- methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
- methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such
- Glycol, methyl isobutyl carbinol, triethylene glycol and the like, and amides preferably include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
- the base eg, organic base
- the base described above can be used as the solvent and the base.
- 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 organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more of the total mass of the treatment liquid.
- Organic solvents are more preferred.
- 100% by mass of the treatment liquid may be an organic solvent.
- the treatment liquid may further contain other components.
- Other components include, for example, known surfactants and known antifoaming agents.
- the method of supplying the processing liquid is not particularly limited as long as the processing liquid can be brought into contact with the pattern obtained in the developing step. be done.
- the supply method is not particularly limited, and includes a method of immersing the substrate in the processing liquid, a method of supplying the substrate with a paddle (liquid heap), a method of supplying the processing liquid to the substrate by showering, and a method of supplying the processing liquid onto the substrate.
- a method of continuously supplying the processing liquid using a nozzle is preferable, and the method of supplying the processing liquid to the image area is preferred.
- a method in which the treatment liquid supplied from the nozzle is kept on the substrate is more preferable.
- the above treatment liquid supply methods (for example, a combination of paddle supply and shower supply, paddle supply and straight nozzle supply) may be used in combination.
- paddle feeding has the effect of swelling the membrane and making it easier for the subsequent treatment liquid to permeate.
- the treatment liquid may be used in at least one of the combined methods.
- the treatment process using the treatment liquid may be performed.
- Preferred aspects of the treatment liquid that does not contain a base and a base generator are the same as preferred aspects of the rinsing solution in other rinsing steps described later.
- the method of supplying the processing liquid containing no base and base generator onto the pattern in the above embodiment is not particularly limited, but a method of supplying with a paddle can be mentioned.
- the method of supplying the treatment liquid onto the pattern in the above-described mode is not particularly limited, but preferred examples include supply by a shower, supply by a straight nozzle, and the like.
- a base-free treatment liquid from the paddle
- the pattern swells, and at least one compound selected from the group consisting of bases and base generators in the treatment liquid to be supplied later easily permeates into the pattern. It is considered that the effect such as improvement of elongation at break is more likely to be obtained.
- the processing liquid from a shower, a straight nozzle, or the like the removability (rinsability) of development scum and the like may be excellent.
- the method of supplying the processing liquid in the processing step includes a process in which the processing liquid is continuously supplied to the substrate, a process in which the processing liquid is kept in a substantially stationary state on the substrate, and a process in which the processing liquid is kept on the substrate 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 processing step is preferably a step of showering or continuously supplying the processing liquid to the pattern after development. It is also preferable that development in the development step is performed by puddle development, and at least one supply of the processing liquid in the processing step is performed by shower supply or continuous supply by a straight nozzle or the like.
- the puddle development swells the pattern, which facilitates penetration of at least one compound selected from the group consisting of bases and base generators in the processing liquid into the pattern, thereby improving elongation at break and the like. It is considered that the effect of is more likely to be obtained.
- the treatment time in the treatment step (that is, the time during which the treatment liquid is in contact with the pattern) is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the treatment solution during the treatment step is not particularly defined, but it is preferably 10 to 45°C, more preferably 18 to 30°C.
- the method for producing a cured product of the present invention includes a rinsing step (hereinafter also referred to as "another rinsing step") in which the pattern (pattern obtained by the developing step) is washed with a rinsing solution that does not contain a base or a base generator. ) may be included.
- the method for producing a cured product of the present invention can include other rinsing steps, for example, before the processing steps described above and after the developing steps described above.
- the method for producing a cured product of the present invention does not include the above-described treatment step, it can be included after the above-described development step and before the above-described heating step.
- the same liquid as the above-described treatment liquid can be used except that it does not contain a base and a base generator. It is the same as the preferred embodiment of each component other than the base and the base generator contained in the liquid. Also, the rinse liquid can be supplied to the pattern in the same manner as the treatment liquid described above.
- the pattern obtained by the development step (when the rinse step is performed, the pattern after rinsing) may be subjected to a post-development exposure step of exposing the pattern after the development step.
- the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by 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 that the entire pattern be exposed.
- 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 film after the heating step is heated from 25 ° C. to 260 ° C. at a rate of 10 ° C./min, maintained at 260 ° C. for 15 minutes, and heated from 260 ° C. to 300 ° C. at 10 ° C./min.
- the mass reduction rate represented by the formula A when the temperature is increased at a rate of 10 minutes is 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less.
- the mass reduction rate is measured by the method described in Examples below.
- the cyclization rate of the cyclized resin obtained from the cyclized resin precursor in the resulting cured product is 95% or more, preferably 98% or more, and preferably 99%. It is more preferable to be above.
- the upper limit of the cyclization rate is not particularly limited, and may be 100%.
- the above cyclization rate is calculated by the following method.
- the precursor of the cyclized resin is a polyimide precursor or a polyamideimide precursor
- the infrared absorption spectrum of the film after the heating step is measured, and the peak intensity P1 near 1377 cm -1 which is an absorption peak derived from the imide structure is measured. demand.
- the infrared absorption spectrum is measured again to obtain the peak intensity P2 near 1377 cm ⁇ 1 .
- the precursor of the cyclized resin is a polybenzoxazole precursor
- the peak intensity Q1 near 1650 cm ⁇ 1 which is the absorption peak derived from the amide structure of the film after the heating step, is obtained.
- normalization is performed by the absorption intensity of the aromatic ring seen around 1490 cm ⁇ 1 .
- the infrared absorption spectrum is measured again, the peak intensity Q2 near 1650 cm ⁇ 1 is obtained, and the aromatic ring seen near 1490 cm ⁇ 1 is measured. Normalize by absorption intensity.
- the cyclization rate oxazole conversion rate
- Oxazolization rate (%) (standardized value of peak intensity Q1/standardized value of peak intensity Q2) x 100
- the cyclization rate imidization rate, oxazolization rate
- compounds having absorption at a wavelength of 1377 cm -1 or 1377 cm -1 or 1490 cm -1 or 1650 cm -1 in the composition for example, phthalimide, etc.
- the peak intensity derived from this compound may be removed as the background.
- 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 of the film before and after the heating step is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
- the shrinkage ratio refers to the percentage of volume change before and after the heating process, and can be calculated from the following formula.
- Shrinkage rate [%] 100 - (volume after heating process / volume before heating process) x 100
- the elongation at break of the cured product is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
- the upper limit of the elongation at break is not particularly limited, it may be, for example, 200% or less.
- the elongation at break can be measured according to JIS (Japanese Industrial Standards) K 6251:2017.
- the glass transition temperature (Tg) of the cured product is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
- the upper limit of the glass transition temperature is not particularly limited, it may be 600° C. or lower, for example.
- the glass transition temperature can be measured according to JIS K 7121:2012.
- Fields to which the cured product of the present invention can be applied include insulating films for electronic 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.
- resin composition used in the method for producing a cured product of the present invention is described below.
- the resin composition in the present invention contains a precursor (specific resin) of a cyclized resin.
- 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.
- cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
- a precursor of a cyclized resin is 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.
- a resin that becomes a cyclized resin by forming a ring structure is more preferable.
- Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition in 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 in the present invention preferably contains a polyimide precursor as the specific resin.
- the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
- the resin composition in 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. Further, if necessary, a sensitizer described later can be included. For example, 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 in the invention preferably contains a photoacid generator, which will be described later. For example, a chemically amplified positive photosensitive film or negative photosensitive film is formed from the resin composition of the present invention.
- 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 —NR z —
- 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
- R z represents a hydrogen atom or a monovalent organic group.
- a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NR Z —, preferably an oxygen atom.
- Rz represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.
- R Z represents a monovalent organic group
- preferred embodiments of R Z are the same as preferred embodiments of Z 1 in formula (3-1) described later.
- 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 heteroatom, and in the cyclic aliphatic group and the aromatic group, the ring-membered hydrocarbon group is a heteroatom.
- Ar is each independently an aromatic group
- L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally 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 and 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 optionally 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 111 preferably contains a group represented by any one of the following formulas (5) to (7), and the following formula (5) It is more preferably a group represented by any one of the formulas (7).
- R 111 is preferably a group represented by the following formula (5) from the viewpoint of suppression of film shrinkage during curing.
- Y 1 represents a single bond or a divalent linking group
- Y 2 represents a single bond or a divalent linking group
- * each represents a binding site to another structure.
- Each of the above RNs independently represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
- the above RN is as described above.
- the group represented by formula (7) is preferably a group represented by formula (7-1) below.
- R 111 preferably contains a group represented by the following formula (4), more preferably a group represented by the following formula (4).
- each * represents a binding site with another structure.
- 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 115 specifically 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, or may contain two or more types thereof, as the structure corresponding to R115 .
- 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 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., a 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 (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
- 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.
- 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 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 multiple 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.
- 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 a binding site 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 moiety 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 to 4,000, more preferably 500 to 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 —NR z —
- R 113 represents a hydrogen atom or 1 represents a valent organic group
- Rz represents a hydrogen atom or a monovalent organic group.
- 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 a (ditrifluoromethyl)methylene group 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 , R 113 and R z have the same meanings as R 111 , A 2 , R 113 and R z in formula (2) above, and preferred embodiments are also the same. be.
- 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 a (ditrifluoromethyl)methylene group 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, 1,9
- 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.
- 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 the repeating units represented by the formula (PAI-2), represented by the formula (PAI-1).
- 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, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide precursors as one resin are within the ranges described above.
- the specific resin preferably contains a resin having at least one of repeating units represented by formula (1-1) and repeating units represented by formula (1-2).
- the repeating unit represented by formula (1-1) is a preferred embodiment of the repeating unit represented by formula (2) above
- the repeating unit represented by formula (1-2) is the above
- W 1 represents a divalent organic group
- X 1 represents a tetravalent organic group
- R 1 to R 3 each independently A group represented by the following formula (3-1) or a group represented by the formula (3-2)
- W 2 represents a divalent organic group
- X 2 represents a trivalent organic group.
- the resin is a repeating unit represented by the formula (1-1) in which at least one of R 1 and R 2 is a group represented by the formula (3-1), and a repeating unit represented by the formula (1- 2) in which R 3 is a group represented by formula (3-1).
- Z 1 and Z 2 each independently represent an organic group
- Z 1 and Z 2 may combine to form a ring structure
- a 2 represents an oxygen atom or —NH—
- R 113 represents a hydrogen atom or a monovalent organic group
- * represents a bonding site with another structure.
- R 1 and R 2 are each represented by formula (3-1).
- R 1 and R 2 may be the same group or different groups, as long as they are groups corresponding to the groups described above.
- R 1 and R 2 when both R 1 and R 2 are groups represented by formula (3-2), R 1 and R 2 are each represented by formula (3-2) Any group corresponding to the group may be used, and R 1 and R 2 may be the same group or different groups.
- the cyclization (ring closure) of the specific resin generates a base from the structure represented by the formula (3-1), further promoting the ring closure, so heating at a low temperature of 180 ° C. or less
- a cured product having excellent adhesion to metal can be obtained.
- a residue of the base generator after generation of the base may remain in the cured product.
- the resin has at least one of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2), the remaining resin is the resin after ring closure. Therefore, it is considered that the low-molecular-weight compound remaining in the film after the heating process is eliminated, and the adhesion to the metal is further improved.
- the specific resin When the specific resin has at least one of the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (1-2), the specific resin is a base at any temperature of 120 to 180 ° C. is preferably generated. Further, the specific resin preferably generates a base when heated in the heating step. Whether or not a specific resin generates a base at a certain temperature X°C is judged by the following method. After heating 1 mol of the specific resin under 1 atmospheric pressure in a closed container at the above X° C. for 3 hours, the decomposition amount is quantified by a method such as HPLC (high performance liquid chromatography) to determine whether or not a base is generated. can be done. The amount of the base generated is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the amount of generated base is not particularly limited, but it can be, for example, 1000 mol or less.
- the molecular weight of the base generated from the specific resin is preferably 40-1,000, more preferably 40-500, even more preferably 50-400.
- the boiling point of the base having a pyridine structure at 1 atm is preferably 50 to 600°C, more preferably 50 to 500°C, even more preferably 50 to 450°C.
- 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 expressed by the negative common logarithm pKa of the equilibrium constant Ka.
- pKa is a value calculated by ACD/ChemSketch (registered trademark).
- X 1 has the same definition as R 115 in formula (2), and preferred embodiments are also the same.
- W 1 has the same definition as R 111 in formula (2), and preferred embodiments are also the same.
- RN is as described above.
- the hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group.
- the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-20, more preferably 1-10, and even more preferably 1-8.
- the aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, or may have a structure represented by a combination thereof.
- the aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and still more preferably 6 carbon atoms.
- the hydrocarbon group may have a known substituent as long as the effects of the present invention can be obtained.
- An embodiment in which at least one of Z 1 and Z 2 has a polymerizable group is also one of preferred embodiments of the present invention.
- the polymerizable group include a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and the like, and a radically polymerizable group is preferred.
- the radically polymerizable group is preferably a group having an ethylenically unsaturated group, such as a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, a (meth)allyl group, and the like. mentioned.
- a (meth)acryloxy group is preferable from the viewpoint of reactivity.
- These polymerizable groups may be directly bonded to the nitrogen atom in formula (3-1), or may be bonded via a linking group such as a hydrocarbon group (eg, an alkylene group).
- Z 1 and Z 2 may combine to form a ring structure.
- the ring structure to be formed may be either an aromatic ring structure or an aliphatic ring structure, preferably an aliphatic ring structure, and more preferably a saturated aliphatic ring structure.
- the above ring structure is preferably a cyclic amine having 2 to 10 carbon atoms, and examples thereof include pyrrolidine ring, piperidine ring, morpholine ring, octahydroindole ring, octahydroisoindole ring, pyrrole ring, pyridine ring and the like.
- a ring, a piperidine ring or a morpholine ring are preferred.
- the above ring structure may have a substituent within the range in which the effect of the present invention can be obtained.
- a hydrocarbon group, a halogen atom, etc. are mentioned as a substituent.
- Examples of the ring structure substituted with a substituent include a dimethylpiperidine ring.
- the group represented by formula (3-1) is preferably a group represented by formula (3-1-1) or formula (3-1-2) below.
- Cy represents an aliphatic ring structure or an aromatic ring structure, and * represents a binding site with another structure.
- Z 3 and Z 4 each independently represent an alkyl group, and * represents a bonding site with another structure.
- the ring structure represented by Cy is preferably an aliphatic ring structure, more preferably a saturated aliphatic ring structure.
- the ring structure represented by Cy include pyrrolidine ring, piperidine ring, morpholine ring, octahydroindole ring, octahydroisoindole ring, pyrrole ring, pyridine ring and the like.
- a ring is preferred.
- the ring structure represented by Cy may have a substituent as long as the effect of the present invention can be obtained.
- a hydrocarbon group, a halogen atom, etc. are mentioned as a substituent.
- Examples of the ring structure substituted with a substituent include a dimethylpiperidine ring.
- Z 3 and Z 4 each independently represent an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Alkyl groups of 1 to 8 are more preferred.
- the alkyl group may have a linear, branched, or cyclic structure, or may have a structure represented by a combination thereof.
- a 2 is preferably an oxygen atom.
- R 113 has the same definition as R 113 in formula (2), and preferred embodiments are also the same.
- the specific resin may further contain other repeating units.
- the content of the repeating unit represented by formula (1-1) with respect to all repeating units contained in the specific resin is 50 mol% or more.
- the aspect is also one of the preferred aspects of the present invention.
- the content is preferably 70 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and even more preferably 95 mol % or more.
- the upper limit of the content is not particularly limited, and may be 100 mol %.
- W 2 and R 3 have the same meanings as W 1 and R 2 in formula (1-1), respectively, and preferred embodiments are also the same.
- X 2 has the same definition as R 117 in formula (PAI-2) above, and preferred embodiments are also the same.
- the specific resin may further contain other repeating units.
- Other repeating units include repeating units represented by the above formula (1-1), repeating units represented by the above formula (PAI-1), and the like.
- repeating units represented by formula (1-2) for all repeating units contained in the specific resin, represented by formula (1-1) and the content of repeating units represented by formula (PAI-1) is 50 mol % or more is also one of the preferred embodiments of the present invention.
- the content is preferably 70 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and even more preferably 95 mol % or more.
- the specific resin contains the repeating unit represented by formula (1-2)
- the content of the repeating unit represented by formula (1-2) with respect to all repeating units contained in the specific resin is 50 mol% or more. This aspect is also one of the preferred aspects of the present invention.
- the content is preferably 70 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and even more preferably 95 mol % or more.
- the upper limit of the content is not particularly limited, and may be 100 mol %.
- Total moles of the group represented by the formula (3-1) with respect to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the specific resin The amount ratio is preferably 0.1 mol % or more, more preferably 5 mol % or more, and even more preferably 10 mol % or more.
- the total molar amount of the groups represented by (3-2) above and the total molar amount of the groups represented by formula (3-1) can be calculated, for example, by NMR (nuclear magnetic resonance spectroscopy).
- the group represented by the formula (3-1) contained in the specific resin and The molar ratio of the group represented by formula (3-1) is preferably 99.9 mol% or less, more preferably 95 mol% or less, and further preferably 90 mol% or less. It is preferably 80 mol % or less, and particularly preferably 80 mol % or less.
- the formula (3-1) contained in the specific resin and the molar ratio of the group represented by formula (3-1) to the total molar amount of the group represented by formula (3-2) is preferably 80 mol% or more, It is more preferably 90 mol % or more, still more preferably 95 mol % or more, and particularly preferably 98 mol % or more.
- the molar amount of the group represented by the formula (3-1) with respect to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the specific resin An aspect in which the ratio is 100 mol % is also one of the preferred aspects of the present invention.
- the content molar amount of the group represented by formula (3-1) contained in the specific resin with respect to the total mass of the specific resin is preferably 0.001 to 10 mmol/g, more preferably 0.01 to 5 mmol/g. and more preferably 0.1 to 3 mmol/g. Further, the content mass of the group represented by formula (3-1) contained in the specific resin with respect to the total mass of the specific resin is preferably 0.1 to 70%, and preferably 0.5 to 40%. is more preferred, and 1 to 20% is even more preferred.
- 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 method of reacting 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.
- the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferred.
- 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 In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. 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. is 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., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. 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 compounds of carboxylic acid chlorides 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 compound represented by formula (T-1) may also be used as the terminal blocking agent. By blocking the terminal with such a compound, a structure that easily generates a base can be introduced at the terminal, and even when cured at a low temperature, the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin is increased. likely to increase.
- L T represents a divalent organic group
- Z 1 and Z 2 each independently represent an organic group
- Z 1 and Z 2 combine to form a ring structure. good too.
- L T is preferably a hydrocarbon group and may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group. It is preferably a hydrocarbon group or a cyclic aliphatic hydrocarbon group.
- the linking chain length of L T (that is, the minimum number of atoms among the atoms connecting two carbonyl groups bonded to L T ) is preferably 2 to 4, more preferably 2.
- Z 1 and Z 2 have the same meanings as Z 1 and Z 2 in formula (3-1), and preferred embodiments are also the same.
- an aspect in which at least one of Z 1 and Z 2 has a polymerizable group is also one of preferred aspects of the present invention.
- Examples of the polymerizable group include a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and the like, and a radically polymerizable group is preferred.
- the radically polymerizable group is preferably a group having an ethylenically unsaturated group, such as a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, a (meth)allyl group, and the like. mentioned. Among these, a (meth)acryloxy group is preferable from the viewpoint of reactivity.
- These polymerizable groups may be directly bonded to the nitrogen atom in formula (T-1), or may be bonded via a linking group such as a hydrocarbon group (eg, an alkylene group).
- 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 redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
- the content of the specific resin in the resin composition in 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. more preferably 50% by mass or more, and particularly preferably 70% by mass or more.
- the resin composition in the present invention contains a solvent, and the content of the precursor of the cyclized resin is 70% relative to the total solid content of the resin composition.
- the aspect in which it is at least 10% by mass is also one of the preferred aspects of the present invention.
- the content of the resin in the resin composition in 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 in 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 in the present invention contains at least two kinds of resins.
- the resin composition in 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 in 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 in the present invention may contain the specific resin described above and another resin different from the specific resin (hereinafter also simply referred to as "other resin").
- Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
- phenolic resins polyamides
- epoxy resins polysiloxanes
- resins containing siloxane structures resins containing siloxane structures
- (meth)acrylic resins eth)acrylamide resins
- urethane resins urethane resins
- butyral resins styryl resins
- polyether resins e.g., polyether resins, and polyester resins.
- 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 in 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 in the present invention preferably contains a polymerizable compound.
- Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
- the resin composition in the present invention preferably contains a polymerizable compound having a boiling point of 270° C. or higher at 1 atmosphere.
- the upper limit of the boiling point is not particularly limited, and may be, for example, 500° C. or lower. According to the above aspect, the mass reduction rate described above can be reduced.
- the polymerizable compound having a boiling point of 270° C. or higher at 1 atm is preferably a compound having 3 or more polymerizable groups, more preferably a compound having 4 or more polymerizable groups. is more preferably a compound having 5 or more Although the upper limit of the number of polymerizable groups is not particularly limited, it is preferably 20 or less. Further, the polymerizable compound having a boiling point of 270° C. or higher at 1 atm is preferably a compound having three or more (meth)acrylate groups, and is preferably a compound having four or more (meth)acrylate groups. More preferably, it is a compound having 5 or more (meth)acrylate groups. Although the upper limit of the number of (meth)acrylate groups is not particularly limited, it is preferably 20 or less.
- polymerizable compound having a boiling point of 270° C. or higher at 1 atm examples include dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, ethoxylated dipentaerythritol polymethacrylate, and the like. are mentioned. Further, these compounds can be used as long as they have a boiling point of 270° C. or higher whether they are acrylates or methacrylates. As these compounds, commercial products may be used, for example, those manufactured by Shin-Nakamura Chemical Co., Ltd. may be used.
- the resin composition in 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 in 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 Co., Ltd.
- A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
- dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) ) acrylate (commercially available: KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.)
- their (meth)acryloyl groups are converted via ethylene glycol residues or propylene glycol residues Structures that are linked together are preferred. These oligomeric types can also be used.
- 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 in 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 in the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
- the other cross-linking agent refers to a cross-linking agent other than the above-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.
- 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 in the composition or reaction products thereof. 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 in 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 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 produce 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 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.
- These groups are preferably tertiary alkyl ester groups, acetal ester groups, cumyl ester groups, enol ester groups, and the like. More preferred are tertiary alkyl ester groups and acetal ester 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 an 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, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, Dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril
- Glycoluril-based cross-linking agents such as; urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxy
- benzoguanamine-based cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
- tetramethoxymethylated benzoguanamine monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethyl 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 warping 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 compound compound having an oxetanyl group
- the 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 (these 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, based on the total solid content of the resin composition in 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 in the present invention preferably contains a photosensitizer.
- Photosensitizers include photopolymerization initiators, photoacid generators, and the like, with photopolymerization initiators being preferred.
- the resin composition in the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat.
- a 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.
- 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 initiators examples 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 absorption maximum 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-based 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-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one , and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
- 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 of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
- 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 specific substituents 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 in the present invention. , More preferably 0.5 to 15% by mass, 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, or the like.
- the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed 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, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole,
- 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 in the 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, 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 in the present invention may contain a base generator.
- the base generator is a compound capable of generating a base by physical or chemical action.
- the base generator as used herein does not include the specific resins described above.
- 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, 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 substituents to the extent that 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
- RC1 represents a hydrogen atom or a protecting group
- L represents a divalent linking group
- L is a divalent linking group, preferably a divalent organic group.
- the linking chain length of the linking group is preferably 1 or more, 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 N1 and R 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 are 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 preferably 1 to
- an aliphatic hydrocarbon group as R N1 and R N2 because the generated base is highly basic.
- 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 1 N1 and R 2 N2 are preferably alkyl groups having 5 to 12 carbon atoms.
- 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. is 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 chain alkenylene group, a cyclic alkenylene group, an arylene group and an arylene alkylene 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 linear or branched chain alkenylene group preferably has 1 to 10 C ⁇ C bonds, more preferably 1 to 6, even more preferably 1 to 3.
- 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 even more preferably 6 to 10 carbon atoms.
- the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
- a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a 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 kinds are used, the total amount is preferably within the above range.
- a base can also be generated from the specific resin, or a base or a base generator can be contained in the developer or the processing liquid and permeated into the film. Therefore, compared with a conventional resin composition containing a base generator and a cyclized resin or a precursor thereof, it can be designed to reduce the content of the base generator. As a result, it is believed that the residue of the base generator after base generation, the undecomposed base generator itself and the like are less likely to remain in the composition, and the adhesion to metal and moisture resistance of the cured product are improved. In such an embodiment, it is also preferable to set the content of the base generator to 2% by mass or less with respect to 100 parts by mass of the resin.
- the content of the base generator is preferably 1% by mass or less, more preferably 0.5% by mass or less, relative to 100 parts by mass of the resin. It is also preferable to set the content of the base generator to 0.1% by mass or less with respect to 100 parts by mass of the resin. In these aspects, the lower limit of the content of the base generator may be 0% by mass.
- the content of the base generator can be determined in consideration of the type and amount of base generated from the specific resin, the type and amount of base contained in the developer or processing liquid, heating conditions, and the like.
- the resin composition in 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 in 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 in 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 in 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 aids 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 in 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 in 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 in the present invention preferably contains a polymerization inhibitor.
- Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compound 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 in 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 in the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
- additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
- Organic titanium compounds, antioxidants, anti-agglomerating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (for example, antifoaming agents, flame retardants, etc.) 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 in 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.
- fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (Asahi Glass Co., Ltd.
- Fluorinated 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, the contents of which are incorporated herein.
- a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated herein.
- the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (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
- KP341, 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 KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), 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.
- a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. may be unevenly distributed on the surface of the resin composition of the present invention
- 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 in 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 in 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 in 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 resin composition in 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 resin composition in the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001 with respect to the total solid mass of the resin composition in the present invention. It is preferably from 0.01% by mass to 1% by mass, and more preferably from 0.01% by mass to 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.
- the resin composition in the present invention may contain an antioxidant.
- 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.
- the antioxidant compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein.
- the resin composition in the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which the site functioning as an antioxidant is protected with 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.
- the amount added is 0.1 parts by mass or more, it is easy to obtain the effect of improving elongation characteristics and adhesion to metal materials 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 resin composition in the present invention may or may not contain an anti-aggregation agent, but when it is included, the content of the anti-aggregation agent is 0.01 with respect to the total solid mass of the resin composition in the present invention. It is preferably from 0.02 mass % to 5 mass %, and more preferably from 0.02 mass % to 5 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 resin composition in the present invention may or may not contain a phenolic compound, but when it does, the content of the phenolic compound is 0.01 with respect to the total solid mass of the resin composition in 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.
- the resin composition in the present invention may or may not contain other polymer compounds, but when it does, the content of the other polymer compound is relative to the total solid mass of the resin composition in the present invention. , preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.
- the viscosity of the resin composition in the present invention can be adjusted by 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. If it is 1,000 mm 2 /s or more , it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring. A coating is obtained.
- the water content of the resin composition in 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 in 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.
- the content of the component having a molecular weight of 1000 or less contained in the resin composition, and the content of the component different from the solvent is the total solid content of the resin composition. It is preferably 40% by mass or less.
- the molecular weight is preferably 800 or less, more preferably 600 or less.
- the lower limit of the molecular weight is not particularly limited, it can be, for example, 50 or more.
- the content is preferably 30% by mass or less, more preferably 10% by mass or less.
- the lower limit of the content is not particularly limited, and may be 0% by mass.
- a conventionally known storage container can be used as the storage container for the resin composition in the present invention.
- the inner wall of the container is a multi-layer bottle made 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.
- the resin composition of the present invention is a resin composition containing a precursor of a cyclized resin, wherein at least one of the three films having different thicknesses when subjected to thermal mass measurement under the following measurement conditions 1: rate is 15% by mass or less.
- Mass reduction rate (%) ⁇ 1-(mass of film after heating at 300°C)/(mass of film at 25°C) ⁇ ⁇ 100
- a cured product having excellent adhesion to metal can be obtained.
- the mechanism by which the above effects are obtained is unknown, it is presumed as follows.
- at least one of the three films having different thicknesses has a mass reduction rate of 15% by mass or less when thermomass measurement is performed under the measurement conditions 1 described above.
- the mass reduction rate is 15% by mass or less, it is presumed that the generation of outgassing is suppressed, and therefore the adhesiveness between the cured product and the metal is considered to be excellent.
- the two-hour heating, temperature rise, and maintenance under the above measurement conditions 1 are performed in a nitrogen atmosphere.
- the mass reduction rate is measured by the method described in Examples.
- the cyclization rate of the cured product (cured product before heating from 25 ° C. to 300 ° C. at a rate of 10 ° C./min) obtained under the measurement conditions 1 is preferably 95% or more, and 98%. It is more preferably 99% or more, more preferably 99% or more.
- the upper limit of the cyclization rate is not particularly limited, and may be 100%. Cyclization rate is measured by the method described above. When the cyclization rate is within the above range, the migration of metal ions from the metal layer to the cured product, which uses the uncyclized portion as a permeation path, is also suppressed, and the cured product has even better adhesion to the metal. is obtained.
- the details of the components contained in the resin composition of the present invention, the properties of the resin composition, etc. are the same as the details of the components, the properties of the resin composition, etc. of the resin composition used in the method for producing the cured product of the present invention described above. and preferred embodiments are also the same.
- the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
- the details of the cured product of the present invention are the same as the details of the cured product obtained in the above-described method for producing the cured product of the present invention, and preferred embodiments are also the same.
- 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 laminate of the present invention multiple times.
- the laminate of the present invention includes two or more layers of a cured product obtained by curing a resin composition containing a precursor of a cyclized resin, and at least one of the layers of the cured product is the cured product of the present invention. It is a layer made up of things. Here, it is also one of the preferred embodiments of the present invention that all the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention. It is preferable that the laminate of the present invention includes two or more layers made of the cured material and a metal layer between any of the layers made of the cured material. The metal layer is preferably formed by the metal layer forming step.
- the method for producing the 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 production methods for the cured product that are performed multiple times.
- a metal layer forming step of forming a metal layer on the layer made of the cured product between the production methods for 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. It is preferable that 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 for forming the layer comprising the first cured product and the resin composition of the present invention used for forming the layer comprising 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 manufacturing the 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 of the metal layer By subjecting the surface of the metal layer to the surface activation treatment in this manner, the adhesiveness to the resin composition layer (film) provided on the surface can be improved.
- 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 source 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 description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. The contents of which are incorporated herein.
- SA-1 polyimide precursor
- SA-1 had a weight average molecular weight of 23,100 and a number average molecular weight of 8,900.
- the structure of SA-1 is presumed to be a structure represented by the following formula (SA-1).
- SA-2 to SA-4 ⁇ Synthesis of polyimide precursor resins (SA-2 to SA-4)> The types of amine (pyrrolidine in the synthesis of SA-1) and alcohol (2-hydroxyethyl methacrylate in the synthesis of SA-1) and their molar ratios were changed as shown in the table below, and the carboxylic anhydride (SA- Same as SA-1, except that 4,4'-oxydiphthalic dianhydride in the synthesis of 1) and diamine (4,4'-bis(4-aminophenoxy)biphenyl in the synthesis of SA-1) were changed as appropriate.
- SA-2 to SA-4 were synthesized by the method.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of these resins are shown in the Mw and Mn columns of the table below, respectively.
- the structures of SA-2 to SA-4 are presumed to be structures represented by the following formulas (SA-2) to (SA-4), respectively.
- subscripts in parentheses representing repeating units represent the molar ratio of each repeating unit.
- SA-5 polyimide precursor
- SA-5 polyimide precursor
- the obtained polyimide precursor SA-5 had a weight average molecular weight of 20,200 and a number average molecular weight of 8,100.
- the structure of SA-5 is presumed to be a structure represented by the following formula (SA-5). In the following formula, subscripts in parentheses representing repeating units represent the molar ratio of each repeating unit.
- the obtained polyimide precursor A-1 had a weight average molecular weight of 22,100 and a number average molecular weight of 9,400.
- 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 of each component described in the table was the amount (parts by mass) described in the "addition amount” column of 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 0.5 ⁇ m.
- the description of "-" indicates that the composition does not contain the corresponding component.
- SR-209 (manufactured by Sartomer)
- A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate)
- the curable resin composition layer on the copper substrate is exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/cm 2 using a 100 ⁇ m square photomask for pattern formation, and then the table
- the film was developed for 60 seconds with the developer described in the column “Developer” and rinsed for 30 seconds with the rinse liquid described in the column “Rinse” in the table to obtain a 100 ⁇ m square resin layer.
- the temperature was raised at a temperature increase rate of 10 ° C./min, and after reaching the temperature described in the "Temperature” column of the “Curing conditions” in the table, this temperature was maintained for 2 hours to form a resin film. got 2.
- a shear force was measured on a 100 ⁇ m square resin film 2 on a copper substrate using a bond tester (CondorSigma manufactured by XYZTEC) under an environment of 25° C. and 65% relative humidity (RH). The larger the shearing force, the larger the adhesion force, which is a preferable result.
- the evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Adhesion" column of the table. -Evaluation criteria- A: Shear force exceeds 35 gf B: Shear force exceeds 30 gf and is 35 gf or less C: Shear force exceeds 25 gf and is 30 gf or less D: Shear force is 25 gf or less 1 gf is 0.00980665N.
- Each resin composition or comparative composition prepared in each example and comparative example was applied onto a silicon wafer by spin coating to form a resin composition layer.
- the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a resin composition layer having a uniform thickness of 15 ⁇ m on the silicon wafer.
- a stepper Nekon NSR 2005 i9C
- the entire surface of the resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ/cm 2 . It was developed for 60 seconds with the developer described and rinsed for 30 seconds with the rinse liquid described in the "Rinse" column of the table.
- the rinsed resin composition layer (resin layer) is heated in a nitrogen atmosphere at a rate of temperature increase of 10°C/min, and heated for 2 hours at the temperature described in the "Temperature” column of the “Curing conditions” in the table. Then, a cured layer (resin layer) of the resin composition layer was obtained.
- the cyclization rate and mass reduction rate of the cured layer were the same as the cyclization rate and mass reduction rate of the resin film 2 in the moisture resistance evaluation described above.
- the resulting cured layer was placed in a high temperature and high humidity bath at a temperature of 121 ° C. and a humidity of 100% for 250 hours, and the cured layer before and after the addition was immersed in the following chemicals under the following conditions, and the amount of film thickness was measured.
- Difference in film thickness before and after high temperature and high humidity input A - B
- A Film thickness after immersion in the chemical solution under the above conditions in the cured layer before being put into the high-temperature and high-humidity bath / film thickness before immersion ⁇ 100
- B Film thickness after immersion in the chemical solution under the above conditions / film thickness before immersion in the cured layer after being placed in a high-temperature and high-humidity bath ⁇ 100 -Evaluation criteria- A: The difference in film thickness before and after the high temperature and high humidity application was less than 5%.
- B The difference in film thickness between before and after high temperature and high humidity was 5% or more and less than 10%.
- C The difference in film thickness between before and after high temperature and high humidity was 10% or more and less than 20%.
- D The difference in film thickness between before and after high temperature and high humidity was 20% or more.
- Mass reduction rate (%) ⁇ 1 ⁇ (mass of resin film 2 before temperature rise in (1) above)/(mass of resin film 2 after cooling in (4) above) ⁇ 100
- the resin composition or the comparative composition was applied on a silicon wafer by spin coating to a thickness of 5 ⁇ m, 10 ⁇ m and 20 ⁇ m, respectively, to form resin composition layers with a total of three thicknesses. formed.
- the coating was performed by setting the number of revolutions in the spin coating method to 2000 rpm.
- the solid content concentration of the composition is diluted to 29% by mass with the solvent (solvent listed in the table) contained in each composition, and the rotation speed in the spin coating method is set to 1500 rpm. applied.
- the solid content concentration of the composition is diluted to 29% by mass with the solvent (solvent listed in the table) contained in each composition, and the rotation speed in the spin coating method is set to 3000 rpm. applied.
- Each of the obtained silicon wafers to which the resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a resin composition layer on the silicon wafer.
- the resin composition layer was heated in a nitrogen atmosphere at a heating rate of 10° C./min, reaching 180° C., and then maintained at this temperature for 2 hours to obtain a cured product.
- the 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. 1 to 5 mg of the cured product was weighed into an aluminum pan, and using TG-DTA2500 manufactured by NETZSCH Japan Co., Ltd., the mass reduction rate (%) was measured under the same conditions as in the measurement of the above mass reduction rate (1). It was measured.
- the mass reduction rate was calculated by the following formula and described in the "mass reduction rate" column of the table by the following formula A.
- Mass reduction rate (%) ⁇ 1-(mass of film after heating at 300°C)/(mass of film at 25°C) ⁇ x 100
- the minimum value is shown in the "mass reduction rate (2)" column of the table.
- the mass reduction rate measurement (2) was not evaluated.
- the imidization rate of the cured product with the smallest mass reduction rate is shown in the column of "Imidization rate (2)" in the table. The imidization rate was measured by the same method as the above-mentioned "imidization rate (1)".
- the cured product obtained by the production method of the cured product of the present invention and the cured product composed of the resin composition of the present invention are excellent in adhesion to metals.
- the imidization rate of the cured product obtained is less than 95%
- the resin composition according to Comparative Examples 1 to 5 has a mass reduction rate under measurement condition 1. exceeds 15%. It can be seen that the cured products obtained by the production methods of the cured products according to Comparative Examples 1 to 5 and the cured products composed of the comparative compositions are inferior in adhesion to metals.
- 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 base material on which the thin copper layer was formed, and dried at 100° C. for 4 minutes to obtain a film thickness. After forming a resin composition layer 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 (I-1) for 2 minutes and rinsed with PGMEA (J-1) for 30 seconds to obtain a layer pattern.
- the temperature was raised at a rate of 10° C./min, and after reaching 180° C., the temperature was maintained at 180° C. for 2 hours to form an interlayer insulating film for a rewiring layer.
- 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。
本発明は、金属との密着性に優れた硬化物が得られる硬化物の製造方法、及び、上記硬化物の製造方法を用いた積層体の製造方法及び半導体デバイスの製造方法を提供することを目的とする。
また、本発明は、金属との密着性に優れた硬化物が得られる樹脂組成物、及び、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及び半導体デバイスを提供することを目的とする。
<1> 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、及び、
上記膜を180℃以下の加熱温度で加熱する加熱工程を含む硬化物の製造方法であって、
上記加熱工程後の膜を25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温した際の下記式Aで表される質量減少率が、15%以下であり、
得られる硬化物における、環化樹脂の前駆体から得られる環化樹脂の環化率が95%以上である
硬化物の製造方法。
式A:質量減少率(%)={1-(300℃で加熱した後の膜の質量)/(25℃における膜の質量)}×100
<2> 上記加熱工程における加熱温度が150℃を超える、<1>に記載の硬化物の製造方法。
<3> 上記質量減少率が10%以下である、<1>又は<2>に記載の硬化物の製造方法。
<4> 上記質量減少率が5%以下である、<1>~<3>のいずれか1つに記載の硬化物の製造方法。
<5> 上記環化率が98%以上である、<1>~<4>のいずれか1つに記載の硬化物の製造方法。
<6> 上記加熱工程後の膜がポリイミド膜である、<1>~<5>のいずれか1つに記載の硬化物の製造方法。
<7> 上記膜形成工程と、上記加熱工程との間に、膜を選択的に露光する露光工程を更に含む、<1>~<6>のいずれか1つに記載の硬化物の製造方法。
<8> 上記露光工程と、上記加熱工程との間に、現像液により上記露光後の膜を現像してパターンを形成する現像工程を更に含む、<7>に記載の硬化物の製造方法。
<9> 上記現像液が、有機溶剤を含む、<8>に記載の硬化物の製造方法。
<10> 上記現像工程が、ネガ型のパターンを形成する工程である、<8>又は<9>に記載の硬化物の製造方法。
<11> 上記現像液が塩基を含む、<8>~<10>のいずれか1つに記載の硬化物の製造方法。
<12> 上記現像工程と、上記加熱工程の間に、塩基を含む処理液と上記パターンとを接触させる処理工程を含む、<8>~<11>のいずれか1つに記載の硬化物の製造方法。
<13> 上記樹脂組成物が、感光剤を含む、<1>~<12>のいずれか1つに記載の硬化物の製造方法。
<14> 上記樹脂組成物が、溶剤を含み、上記環化樹脂の前駆体の含有量が、樹脂組成物の全固形分に対して70質量%以上である、<1>~<13>のいずれか1つに記載の硬化物の製造方法。
<15> 上記樹脂組成物が、1気圧における沸点が270℃以上である重合性化合物を含む、<1>~<14>のいずれか1つに記載の硬化物の製造方法。
<16> 上記1気圧における沸点が270℃以上である重合性化合物が、(メタ)アクリレート基を3つ以上有する化合物である、<15>に記載の硬化物の製造方法。
<17> 分子量が1000以下である成分であって、溶剤とは異なる成分の含有量が、樹脂組成物の全固形分に対して30質量%以下である、<1>~<16>のいずれか1つに記載の硬化物の製造方法。
<18> 上記環化樹脂の前駆体が、下記式(1-1)で表される繰り返し単位及び下記式(1-2)で表される繰り返し単位の少なくとも一方を有する樹脂を含む、
<1>~<17>のいずれか1つに記載の硬化物の製造方法。
<19> <1>~<18>のいずれか1つに記載の硬化物の製造方法を複数回繰り返すことを含む、積層体の製造方法。
<20> <1>~<18>のいずれか1つに記載の硬化物の製造方法、又は、<19>に記載の積層体の製造方法を含む、半導体デバイスの製造方法。
<21> 環化樹脂の前駆体を含む樹脂組成物であって、
下記測定条件1で熱質量測定をした場合の厚さの異なる3つの膜のうち、少なくとも1つの質量減少率が15質量%以下である
樹脂組成物;
測定条件1:
上記樹脂組成物をシリコン基板上に5μm、10μm、又は20μmの厚さでそれぞれ塗布し、100℃5分間乾燥した後に180℃、2時間の加熱により硬化物を得て、25℃に戻した上記硬化物を25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温した際の上記硬化物の質量減少率を測定する。
上記質量減少率は、下記式Aにより算出される
式A:質量減少率(%)={1-(300℃で加熱した後の膜の質量)/(25℃における膜の質量)}×100
<22> <21>に記載の樹脂組成物を硬化してなる硬化物。
<23> 環化樹脂の前駆体を含む樹脂組成物を硬化してなる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のうち少なくとも1層が<22>に記載の硬化物からなる層である
積層体。
<24> <22>に記載の硬化物又は<23>に記載の積層体を含む、
半導体デバイス。
また、本発明によれば、金属との密着性に優れた硬化物が得られる樹脂組成物、及び、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及び半導体デバイスが提供される。
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、及び、上記膜を180℃以下の加熱温度で加熱する加熱工程を含む硬化物の製造方法であって、上記加熱工程後の膜を25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温した際の下記式Aで表される質量減少率が、15%以下であり、得られる硬化物における、環化樹脂の前駆体から得られる環化樹脂の環化率が95%以上である。
式A:質量減少率(%)={1-(300℃で加熱した後の膜の質量)/(25℃における膜の質量)}×100
上記効果が得られるメカニズムは不明であるが、以下のように推測される。
本発明の硬化物の製造方法においては、加熱工程における加熱温度が180℃以下であり、加熱工程後の膜を25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温し25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温した際の質量減少率が15%以下であり、かつ、得られる硬化物における、環化樹脂の前駆体から得られる環化樹脂の環化率が95%以上である。
ここで、質量減少率が15%以下である場合、アウトガスの発生が抑制されたと推定されるため、硬化物と金属との密着性に優れると考えられる。
更に、環化率が95%以上である場合、未環化の部分を浸透パスとする金属層から硬化物への金属イオンの移行(マイグレーション)も抑制されると考えられる。
これらの作用により、本発明の硬化物の製造方法によれば、180℃以下という低温での加熱により得られた硬化物であっても、金属との密着性に優れた硬化物が得られると考えられる。
また、本発明の硬化物の製造方法により得られる硬化物は環化率が高いため、耐湿性にも優れると考えられる。
以下、本発明の硬化物の製造方法に含まれる各工程、及び、硬化物の物性について詳細に説明する。
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を含む。
上記樹脂組成物の詳細については後述する。
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、基材の形状によっても塗布方法を適宜選択でき、ウエハ等の円形基材であればスピンコート法、スプレーコート法、インクジェット法等が好ましく、矩形基材であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、500~3,500rpmの回転数で、10秒~3分程度適用することができる。
また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス(EBR)、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。
本発明の硬化物の製造方法は、上記膜を180℃以下の加熱温度で加熱する加熱工程を含む。
ここで、加熱工程における上記膜は、後述する露光工程及び現像工程を経た、現像後の膜(パターン)であってもよいし、後述する露光工程を経て、現像工程を経ていない膜であってもよいし、上述の膜形成工程(及び、必要に応じて上述の乾燥工程)により形成され、他の工程を経ていない膜であってもよい。
また、本発明の硬化物の製造方法においては、加熱工程を含む全工程において膜の温度が180℃以下であることが好ましい。上記態様によれば、基材等の材料への熱による損傷等を抑制することができる。
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、加熱工程においては、後述する特定樹脂、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、20℃~180℃が好ましく、150℃~180℃がより好ましく、160℃~180℃が更に好ましい。
ここで、加熱工程後の膜はポリイミド膜であることが好ましい。具体的には、加熱工程後の膜に含まれる樹脂が、繰返し単位中にイミド環構造を有する樹脂であることが好ましい。
すなわち、加熱工程の前後で、加熱工程後の膜の環化率(すなわち、環化樹脂の前駆体から得られる環化樹脂の環化率)が増加することが好ましい。
具体的には、加熱工程前の膜の環化率(%)を環化率A、加熱工程後の膜の環化率(%)を環化率Bとした場合に、下記式で表される環化率の差が70%以上であることが好ましく、80%以上であることがより好ましく、90%以上であることが更に好ましい。上記環化率の上限は特に限定されず、100%であってもよい。
環化率の差=環化率B-環化率A
膜の環化率の測定方法については後述する。
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1~30℃/秒の昇温速度で行うことが好ましく、2~20℃/秒がより好ましく、3~10℃/秒が更に好ましい。
また、最高加熱温度を維持する際の温度の振れ幅(最高温度での加熱時間における温度の最大値と最小値の差)は、0.1℃~20℃が好ましく、0.1~10℃がより好ましく、0.1℃~3℃がより好ましい。
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は、常圧下で行ってもよいし、減圧下で行ってもよい。加熱を減圧下で行う場合、加熱の開始前に減圧が完了されてもよく、加熱開始から昇温中に減圧が完了されてもよく、最高加熱温度に達した後に減圧が完了されてもよく、減圧の完了のタイミングは特に限定されない。減圧の完了とは、圧力が20mmHg(体積比)以下になることをいう。上記圧力は差圧計により測定できる。ここで、最高加熱温度を維持する時間の全てにおいて上記膜が減圧下にあることも好ましい態様である。 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。
上記膜形成工程後、上記加熱工程前の上記膜は、膜を選択的に露光する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、上記膜形成工程と、上記加熱工程との間に、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んでもよい。
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、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、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。
露光後加熱工程の前後では、加熱工程後の膜の環化率(すなわち、環化樹脂の前駆体から得られる環化樹脂の環化率)が実質的に増加しないことも好ましい。
具体的には、上述の環化率の差が30%以下であることも好ましく、20%以下であることもより好ましく、10%以下であることも更に好ましい。上記環化率の上限は特に限定されず、0%であってもよい。
特に、上記膜が後述する光塩基発生剤を含まない場合、上述の環化率の差が30%以下であることが好ましく、20%以下であることがより好ましく、10%以下であることが更に好ましい。上記環化率の上限は特に限定されず、0%であってもよい。
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んでもよい。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、形成されるパターンをネガ型のパターンという。また、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い、形成されるパターンをポジ型のパターンという。
本発明において、現像工程は、ネガ型のパターンを形成する工程であることが好ましい。
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、有機溶剤を含む現像液であることが好ましい。
また、現像液が有機溶剤を含む場合、現像液の全質量に対する水の含有量は、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記水の含有量は、特に限定されず、0質量%であってもよい。
上記態様によれば、現像工程において現像液中の塩基又は塩基発生剤が膜中に浸透し、続く加熱工程において、上記塩基又は上記塩基発生剤から発生する塩基の作用により環化樹脂の前駆体の環化が促進されると考えられる。
その結果、加熱工程後の環化樹脂の前駆体から得られる環化樹脂の環化率が増大し、180℃以下という低温で加熱した場合であっても、金属と硬化物との密着性が向上すると考えられる。
上記態様において、長期間における金属と硬化物との密着性の観点からは、現像液は、塩基を含むことが好ましい。
また、上記態様において、現像液は有機溶剤を含む現像液であることが好ましい。
好ましい塩基としては、硬化物に残存した場合の信頼性(硬化物を更に加熱した場合の基材との密着性)の観点からは、有機塩基が好ましい。
また、塩基としては、アミノ基を有する塩基が好ましく、1級アミン、2級アミン、3級アミン、アンモニウム塩、3級アミドなどが好ましいが、イミド化反応を促進する為には、1級アミン、2級アミン、3級アミンが好ましく、2級アミン又は3級アミンがより好ましく、3級アミンが最も好ましい。
塩基としては、硬化物の機械特性(破断伸び)の観点からは、得られる硬化物中に残存しにくいものが好ましく、環化(イミド化)促進の観点からは、揮発、気化等により、加熱前に残存量が減少しにくいものであることが好ましい。
したがって、塩基の沸点は、常圧(101,325Pa)で30℃から350℃であることが好ましく、80℃~270℃であることがより好ましく、100℃~230℃であることが更に好ましい。
また、塩基の沸点は、現像液に含まれる有機溶剤の沸点から20℃を減算した温度よりも高いことが好ましく、現像液に含まれる有機溶剤の沸点よりも高いことがより好ましい。
例えば、有機溶剤の沸点が100℃である場合、使用される塩基は、沸点が80℃以上であることが好ましく、沸点が100℃以上であることがより好ましい。
上記塩基の共役酸がDMSO中のpKaを複数有する場合、その中の少なくとも1つが上記範囲内であることが好ましい。
ここで、上記pKaとは、酸の第一解離定数の逆数の対数を表し、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値をpKaとして用いることとする。
また、塩基が10~30℃において液体ではない場合、塩基の含有量は0.3~30質量%であることが好ましく、0.5~20質量%であることがより好ましい。
塩基は、1種単独で用いてもよいし、2種以上を併用してもよい。現像液において2種以上の塩基を併用する場合、それらの合計含有量が上述の範囲内であることが好ましい。
現像液は、塩基発生剤を含んでもよい。
塩基発生剤としては、光塩基発生剤又は熱塩基発生剤が挙げられ、熱塩基発生剤が好ましい。
上記光塩基発生剤又は熱塩基発生剤としては、例えば、後述の樹脂組成物に含まれる成分として説明した塩基発生剤を、特に制限なく使用することができる。
塩基発生剤は、1種単独で用いてもよいし、2種以上を併用してもよい。現像液において2種以上の塩基発生剤を併用する場合、それらの合計含有量が上述の範囲内であることが好ましい。
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。
本発明の硬化物の製造方法は、現像工程と、加熱工程との間に、塩基及び塩基発生剤よりなる群から選ばれた少なくとも1種の化合物を含む処理液と上記パターンとを接触させる処理工程を含むことが好ましく、現像工程と、加熱工程との間に、塩基を含む処理液と上記パターンとを接触させる処理工程を含むことがより好ましい。
このような態様によれば、処理液に含まれる塩基及び塩基発生剤よりなる群から選ばれた少なくとも1種の化合物が現像後のパターンに浸透すると考えられる。
その結果、加熱工程後の環化樹脂の前駆体から得られる環化樹脂の環化率が増大し、180℃以下という低温で加熱した場合であっても、金属と硬化物との密着性が向上すると考えられる。
また、処理液は、リンス液であることが好ましい。
更に、上記処理液がリンス液であり、かつ、上記処理工程が、上記リンス液でパターンを洗浄するリンス工程であることが好ましい。
すなわち、上記処理工程は、塩基及び塩基発生剤よりなる群から選ばれた少なくとも1種の化合物を含むリンス液で上記パターン(現像工程により得られたパターン)を洗浄するリンス工程であることが好ましい。
また、上記処理工程は、例えば、後述する「他のリンス工程」の後に行われてもよい。
処理液の全質量に対する水の含有量は、50質量%以下であることが好ましく、20質量%以下であることが好ましく、10質量%以下であることがより好ましく、5質量%以下であることが更に好ましく、2質量%以下であることが特に好ましい。上記水の含有量の下限は、特に限定されず、0質量%であってもよい。
処理液が塩基を含む場合、処理液に含まれる塩基は、常圧(101,325Pa)における沸点が300℃以下であることが好ましく、250℃以下であることがより好ましく、180℃以下であることが更に好ましい。上記沸点の下限は特に限定されないが、処理液が有機溶剤を含む場合、上記有機溶剤の沸点(有機溶剤を複数種含む場合は、それらの沸点のうち最低のもの)から20℃を減算した温度よりも高いことが好ましく、処理液に含まれる有機溶剤の沸点よりも高いことがより好ましい。
例えば、有機溶剤の沸点が100℃である場合、使用される塩基は、沸点が80℃以上であることが好ましく、沸点が100℃以上であることがより好ましい。
その他、処理液に含まれる塩基の好ましい態様は、上述の現像液に含まれる塩基の好ましい態様と同様である。
また、塩基が10~30℃において液体ではない場合、塩基の含有量は0.3~30質量%であることが好ましく、0.5~20質量%であることがより好ましい。
塩基は、1種単独で用いてもよいし、2種以上を併用してもよい。処理液において2種以上の塩基を併用する場合、それらの合計含有量が上述の範囲内であることが好ましい。
処理液は、塩基発生剤を含んでもよい。
塩基発生剤としては、光塩基発生剤又は熱塩基発生剤が挙げられ、熱塩基発生剤が好ましい。
上記光塩基発生剤又は熱塩基発生剤としては、例えば、後述の樹脂組成物に含まれる成分として説明した光塩基発生剤又は熱塩基発生剤を、特に制限なく使用することができる。
塩基発生剤は、1種単独で用いてもよいし、2種以上を併用してもよい。処理液において2種以上の塩基発生剤を併用する場合、それらの合計含有量が上述の範囲内であることが好ましい。
また、上述の塩基(例えば、有機塩基)が処理液が使用される環境において液体の場合、上述の塩基を溶剤及び塩基として使用することができる。
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。
処理液の供給方法としては、処理液と、現像工程で得られたパターンとを接触させることができれば特に限定されないが、例えば、現像工程で得られたパターン上に処理液を供給する態様が挙げられる。上記供給方法としては、特に制限は無く、基材を処理液に浸漬する方法、基材上でのパドル(液盛り)による供給、基材に処理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処理液を連続供給する方法がある。
処理液の画像部への浸透性、製造上の効率の観点から、処理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、ノズルにて連続供給する方法が好ましく、画像部への処理液の浸透性の観点からは、ノズルで供給された処理液が基材上に保たれる方法がより好ましい。
上記処理液の供給方法(例えば、パドルによる供給とシャワーによる供給、パドルによる供給とストレートノズルによる供給の組み合わせ)は併用して行っても良い。例えば、パドル供給には、膜が膨潤して後の処理液が浸透しやすくなる効果がある。また、処理液は少なくとも併用する方法の1つに使用していればよい。ここで、本発明において、塩基及び塩基発生剤を含まない処理液(例えば、後述の他のリンス工程におけるリンス液)をパターン上に供給した後(例えば、後述の他のリンス工程において、リンス液をパターン上に供給し、パターンを洗浄した後)に、処理液による処理工程を行う態様としてもよい。塩基及び塩基発生剤を含まない処理液の好ましい態様は、後述の他のリンス工程におけるリンス液の好ましい態様と同様である。
上記態様における塩基及び塩基発生剤を含まない処理液をパターン上に供給する方法としては、特に限定されないが、パドルによる供給が挙げられる。
上記態様における処理液をパターン上に供給する方法としては、特に限定されないが、シャワーによる供給、ストレートノズルによる供給等が好ましく挙げられる。
塩基を含まない処理液をパドルにより供給することにより、パターンが膨潤して後に供給される処理液中の塩基及び塩基発生剤よりなる群から選ばれた少なくとも1種の化合物がパターンに浸透しやすくなり、破断伸びの向上等の効果がより得られやすくなると考えられる。また、処理液をシャワー、ストレートノズル等により供給することにより、現像カスなどの除去性(リンス性)にも優れる場合がある。
また処理工程における処理液の供給方法としては、処理液が連続的に基材に供給され続ける工程、基材上で処理液が略静止状態で保たれる工程、基材上で処理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。
これらの中でも、処理工程は、処理液を現像後のパターンに対してシャワーにより供給、又は、連続供給する工程であることが好ましい。
また、現像工程における現像をパドル現像により行い、かつ、処理工程における処理液の供給のうち、少なくとも1回をシャワーによる供給、又は、ストレートノズル等による連続供給により行うことも好ましい。上記態様によれば、パドル現像によりパターンが膨潤することにより、処理液中の塩基及び塩基発生剤よりなる群から選ばれた少なくとも1種の化合物がパターンに浸透しやすくなり、破断伸びの向上等の効果がより得られやすくなると考えられる。
本発明の硬化物の製造方法は、塩基及び塩基発生剤のいずれをも含まないリンス液で上記パターン(現像工程により得られたパターン)を洗浄するリンス工程(以下、「他のリンス工程」ともいう。)を含んでもよい。
本発明の硬化物の製造方法は、他のリンス工程を、例えば、上述の処理工程の前、上述の現像工程の後に含むことができる。また、本発明の硬化物の製造方法が、上述の処理工程を含まない場合、上述の現像工程の後、上述の加熱工程の前に含むことができる。
他のリンス工程におけるリンス液としては、塩基及び塩基発生剤を含まない以外は、上述の処理液と同様の液体を用いることができ、リンス液に含まれる各成分の好ましい態様は、上述の処理液に含まれる塩基及び塩基発生剤以外の各成分の好ましい態様と同様である。
また、リンス液は、上述の処理液と同様の方法により、パターンに供給することができる。
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。
〔質量減少率〕
本発明の硬化物の製造方法において、加熱工程後の膜を25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温した際の式Aで表される質量減少率は、15質量%以下であり、10質量%以下であることが好ましく、5質量%以下であることが更に好ましい。
質量減少率は、後述する実施例に記載の方法により測定される。
本発明の硬化物の製造方法において、得られる硬化物における、環化樹脂の前駆体から得られる環化樹脂の環化率は95%以上であり、98%以上であることが好ましく、99%以上であることがより好ましい。上記環化率の上限は特に限定されず、100%であってもよい。
上記環化率は、下記方法により算出される。
環化樹脂の前駆体がポリイミド前駆体又はポリアミドイミド前駆体である場合、加熱工程後の膜の赤外吸収スペクトルを測定し、イミド構造由来の吸収ピークである1377cm-1付近のピーク強度P1を求める。次に、その加熱工程後の膜を350℃で1時間熱処理した後、再度、赤外吸収スペクトルを測定し、1377cm-1付近のピーク強度P2を求める。得られたピーク強度P1、P2を用い、下記式に基づいて、環化率(イミド化率)を求めることができる。
イミド化率(%)=(ピーク強度P1/ピーク強度P2)×100
環化樹脂の前駆体がポリベンゾオキサゾール前駆体である場合、上記加熱工程後の膜の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を求める。次に、1490cm-1付近に見られる芳香環の吸収強度で規格化する。次に、上記加熱工程後の膜を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する。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、環化率(オキサゾール化率)を求めることができる。
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
また、上記環化率(イミド化率、オキサゾール化率)の測定において、組成物中に1377cm-1若しくは1377cm-1、又は、1490cm-1若しくは1650cm-1の波長に吸収を有する化合物(例えば、フタルイミドなど)を含む場合、この化合物由来のピーク強度をバックグラウンドとして除けばよい。
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。
また、上記加熱工程の前後における膜の収縮率は、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、加熱工程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-(加熱工程後の体積÷加熱工程前の体積)×100
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。上記ガラス転移温度の上限は特に限定されないが、例えば、600℃以下であればよい。ガラス転移温度は、JIS K 7121:2012に準拠して測定することができる。
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、電子デバイスの絶縁膜、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。
以下、本発明の硬化物の製造方法において用いられる樹脂組成物について説明する。
本発明における樹脂組成物は、環化樹脂の前駆体(特定樹脂)を含む。
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、本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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。
また、特定樹脂は重合性基を有することが好ましく、ラジカル重合性基を含むことがより好ましい。
特定樹脂がラジカル重合性基を有する場合、本発明における樹脂組成物は、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。このような本発明における樹脂組成物からは、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、本発明における樹脂組成物は、後述の光酸発生剤を含むことが好ましい。このような本発明における樹脂組成物からは、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。
Rzは水素原子又は1価の有機基を表し、水素原子が好ましい。Rzが1価の有機基を表す場合、RZの好ましい態様は、後述する式(3-1)におけるZ1の好ましい態様と同様である。
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、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-又は-NHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。
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。
これらの中でも、硬化時における膜の収縮の抑制の観点からは、R111は下記式(5)で表される基であることが好ましい。
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。
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。
式(2-A)
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。
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。
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。
ここで、式(1-1)で表される繰返し単位は上述の式(2)で表される繰返し単位の好ましい一態様であり、式(1-2)で表される繰返し単位は上述の式(PAI-2)で表される繰返し単位の好ましい一態様である。
また、式(1-1)において、R1及びR2がいずれも式(3-1)で表される基である場合、R1とR2とはそれぞれが式(3-1)で表される基に該当する基であればよく、R1及びR2は同一の基であってもよいし、異なる基であってもよい。
式(1-1)において、R1及びR2がいずれも式(3-2)で表される基である場合、R1とR2とはそれぞれが式(3-2)で表される基に該当する基であればよく、R1及びR2は同一の基であってもよいし、異なる基であってもよい。
また、例えば後述する塩基発生剤を用いた場合には、塩基発生剤の塩基を発生した後の残存物が硬化物中に残存する場合が有る。しかし、式(1-1)で表される繰り返し単位及び式(1-2)で表される繰り返し単位の少なくとも一方を有する樹脂であれば、残存するものは閉環後の樹脂である。そのため、加熱工程後に膜に低分子化合物が残存することが解消され、金属との密着性がより向上すると考えられる。
また、特定樹脂は上記加熱工程における加熱において塩基を発生することが好ましい。
特定樹脂がある温度X℃で塩基を発生するか否かは、下記方法により判断される。
1モルの特定樹脂を密閉容器中1気圧下、上記X℃、3時間の加熱後に、HPLC(高速液体クロマトグラフィ)などの方法で分解量を定量し、塩基が発生するか否かを判定することができる。上記塩基の発生量は0.1モル以上であることが好ましく、0.5モル以上であることがより好ましい。上記塩基の発生量の上限は特に限定されないが、例えば1000モル以下とすることができる。
上記ピリジン構造を有する塩基の1気圧における沸点は、50~600℃が好ましく、50~500℃がより好ましく、50~450℃が更に好ましい。
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。
式(1-1)中、W1は式(2)中のR111と同義であり、好ましい態様も同様である。
上記炭化水素基としては、脂肪族炭化水素基、芳香族炭化水素基のいずれであってもよいが、脂肪族炭化水素基が好ましく、飽和脂肪族炭化水素基がより好ましい。
上記脂肪族炭化水素基の炭素数は、1~20が好ましく、1~10がより好ましく、1~8が更に好ましい。
また、上記脂肪族炭化水素基は、直鎖状、分岐鎖状又は環状のいずれの構造であってもよいし、これらの組み合わせにより表される構造であってもよい。
上記芳香族炭化水素基の炭素数は、6~20が好ましく、6~10がより好ましく、6が更に好ましい。
上記炭化水素基は、本発明の効果が得られる範囲内で公知の置換基を有してもよい。
重合性基としては、ラジカル重合性基、エポキシ基、オキセタニル基、メチロール基、アルコキシメチル基などが挙げられ、ラジカル重合性基が好ましい。
ラジカル重合性基としては、エチレン性不飽和基を有する基が好ましく、(メタ)アクリロキシ基、(メタ)アクリルアミド基、ビニルフェニル基、マレイミド基、スチリル基、ビニル基、(メタ)アリル基などが挙げられる。
これらの中でも、反応性の観点からは、(メタ)アクリロキシ基が好ましい。
これらの重合性基は、式(3-1)中の窒素原子と直接結合していてもよいし、炭化水素基(例えば、アルキレン基)等の連結基を介して結合していてもよい。
形成される環構造としては、芳香族環構造であっても脂肪族環構造であってもよいが、脂肪族環構造であることが好ましく、飽和脂肪族環構造であることがより好ましい。
上記環構造としては、炭素数2~10の環状アミンが好ましく、例えば、ピロリジン環、ピペリジン環、モルホリン環、オクタヒドロインドール環、オクタヒドロイソインドール環、ピロール環、ピリジン環などが挙げられ、ピロリジン環、ピペリジン環又はモルホリン環が好ましい。
また、上記環構造は本発明の効果が得られる範囲において置換基を有してもよい。置換基としては、炭化水素基、ハロゲン原子等が挙げられる。置換基により置換された環構造としては、例えば、ジメチルピペリジン環などが挙げられる。
式(3-1-2)中、Z3及びZ4はそれぞれ独立に、アルキル基を表し、*は他の構造との結合部位を表す。
上記Cyで表される環構造としては、例えば、ピロリジン環、ピペリジン環、モルホリン環、オクタヒドロインドール環、オクタヒドロイソインドール環、ピロール環、ピリジン環などが挙げられ、ピロリジン環、ピペリジン環又はモルホリン環が好ましい。
また、上記Cyで表される環構造は本発明の効果が得られる範囲において置換基を有してもよい。置換基としては、炭化水素基、ハロゲン原子等が挙げられる。置換基により置換された環構造としては、例えば、ジメチルピペリジン環などが挙げられる。
上記アルキル基は、直鎖状、分岐鎖状又は環状のいずれの構造であってもよいし、これらの組み合わせにより表される構造であってもよい。
式(3-2)中、R113は式(2)中のR113と同義であり、好ましい態様も同様である。
特定樹脂が式(1-1)で表される繰返し単位を含む場合、特定樹脂に含まれる全繰返し単位に対する式(1-1)で表される繰返し単位の含有量が50モル%以上である態様も、本発明の好ましい態様の1つである。
また、上記含有量は、70モル%以上であることが好ましく、80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、95モル%以上であることが更に好ましい。
上記含有量の上限は特に限定されず、100モル%であってもよい。
式(1-2)中、X2は上述の式(PAI-2)におけるR117と同義であり、好ましい態様も同様である。
特定樹脂が式(1-2)で表される繰返し単位を含む場合、特定樹脂は、他の繰返し単位を更に含んでもよい。
他の繰返し単位としては、上述の式(1-1)で表される繰返し単位、上述の式(PAI-1)で表される繰返し単位等が挙げられる。
また、上記含有量は、70モル%以上であることが好ましく、80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、95モル%以上であることが更に好ましい。
また、特定樹脂が式(1-2)で表される繰返し単位を含む場合、特定樹脂に含まれる全繰返し単位に対する式(1-2)で表される繰返し単位の含有量が50モル%以上である態様も、本発明の好ましい態様の1つである。
また、上記含有量は、70モル%以上であることが好ましく、80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、95モル%以上であることが更に好ましい。
上記含有量の上限は特に限定されず、100モル%であってもよい。
上記(3-2)で表される基の総モル量、及び、式(3-1)で表される基の総モル量は、例えばNMR(核磁気共鳴装置)により算出することができる。
また、耐薬品性、パターン形成性を向上させる理由から、特定樹脂に含まれる式(3-1)で表される基、及び、式(3-2)で表される基の総モル量に対する式(3-1)で表される基のモル量の割合は、99.9モル%以下であることが好ましく、95モル%以下であることがより好ましく、90モル%以下であることが更に好ましく、80モル%以下であることが特に好ましい。
また、ポリイミド前駆体樹脂、ポリアミドイミド前駆体樹脂の環化を促進して、加熱工程における加熱温度を低温化し、破断伸びを向上させる理由から、特定樹脂に含まれる式(3-1)で表される基、及び、式(3-2)で表される基の総モル量に対する式(3-1)で表される基のモル量の割合が、80モル%以上であることが好ましく、90モル%以上であることがより好ましく、95モル%以上であることが更に好ましく、98モル%以上であることが特に好ましい。特定樹脂に含まれる式(3-1)で表される基、及び、式(3-2)で表される基の総モル量に対する式(3-1)で表される基のモル量の割合は100モル%である態様も本発明の好ましい態様の一つである。
また、特定樹脂の総質量に対する特定樹脂に含まれる式(3-1)で表される基の含有質量は、0.1~70%であることが好ましく、0.5~40%であることがより好ましく、1~20%であることが更に好ましい。
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。
LTにおける連結鎖長(すなわち、LTと結合する2つのカルボニル基を結ぶ原子数のうち、最小の原子数)は、2~4であることが好ましく、2であることがより好ましい。
式(T-1)中、Z1及びZ2は、式(3-1)中のZ1及びZ2と同義であり、好ましい態様も同様である。
特に、Z1及びZ2の少なくとも一方が重合性基を有する態様も、本発明の好ましい態様の1つである。
重合性基としては、ラジカル重合性基、エポキシ基、オキセタニル基、メチロール基、アルコキシメチル基などが挙げられ、ラジカル重合性基が好ましい。
ラジカル重合性基としては、エチレン性不飽和基を有する基が好ましく、(メタ)アクリロキシ基、(メタ)アクリルアミド基、ビニルフェニル基、マレイミド基、スチリル基、ビニル基、(メタ)アリル基などが挙げられる。
これらの中でも、反応性の観点からは、(メタ)アクリロキシ基が好ましい。
これらの重合性基は、式(T-1)中の窒素原子と直接結合していてもよいし、炭化水素基(例えば、アルキレン基)等の連結基を介して結合していてもよい。
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。
本発明における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く、70質量%以上であることが特に好ましい。
ここで、硬化物の金属との密着性の観点からは、本発明における樹脂組成物が溶剤を含み、上記環化樹脂の前駆体の含有量が、樹脂組成物の全固形分に対して70質量%以上である態様も、本発明の好ましい態様の1つである。
また、本発明における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。
本発明における樹脂組成物は、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、本発明における樹脂組成物は、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。
本発明における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。
本発明における樹脂組成物は、上述した特定樹脂と、特定樹脂とは異なる他の樹脂(以下、単に「他の樹脂」ともいう)とを含んでもよい。
他の樹脂としては、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、(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。
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、本発明における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、本発明における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。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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。
また、上記沸点の上限は特に限定されず、例えば500℃以下であればよい。
上記態様によれば、上述の質量減少率を低くすることができる。
また、上記1気圧における沸点が270℃以上である重合性化合物は、(メタ)アクリレート基を3つ以上有する化合物であることが好ましく、(メタ)アクリレート基を4つ以上有する化合物であることがより好ましく、(メタ)アクリレート基を5つ以上有する化合物であることが更に好ましい。上記(メタ)アクリレート基の数の上限は、特に限定されないが、20個以下であることが好ましい。
また、これらの化合物は、アクリレートであってもメタクリレートであっても沸点が270℃以上であれば使用可能である。
これらの化合物としては市販品を用いてもよく、例えば、新中村化学工業(株)製のものを用いることができる。
本発明における樹脂組成物は、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、本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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、本発明における樹脂組成物は、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。
ジメトキシメチル化ベンゾグアナミン、トリメトキシメチル化ベンゾグアナミン、テトラエトキシメチル化ベンゾグアナミン、モノプロポキシメチル化ベンゾグアナミン、ジプロポキシメチル化ベンゾグアナミン、トリプロポキシメチル化ベンゾグアナミン、テトラプロポキシメチル化ベンゾグアナミン、モノブトキシメチル化ベンゾグアナミン、ジブトキシメチル化ベンゾグアナミン、トリブトキシメチル化ベンゾグアナミン、テトラブトキシメチル化ベンゾグアナミ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、本発明における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。
感光剤としては、光重合開始剤、光酸発生剤等が挙げられ、光重合開始剤が好ましい。
本発明における樹脂組成物は、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、アンスラピリドン系、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)ベンズチアゾール、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。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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。ここでいう塩基発生剤には、上述の特定樹脂は含まれないものとする。本発明における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。
また、上述の通り、本発明においては、特定樹脂からも塩基が発生する、又は、現像液若しくは処理液に塩基又は塩基発生剤を含有させ、膜に浸透させることもできる。
そのため、従来の塩基発生剤及び環化樹脂又はその前駆体を含む樹脂組成物と比較して、塩基発生剤の含有量を減少させる設計とすることができる。その結果、塩基発生剤の塩基発生後の残存物、未分解の塩基発生剤自体等が組成物中に残りにくくなり、硬化物の金属との密着性及び耐湿性が向上すると考えられる。
このような態様において、塩基発生剤の含有量を、樹脂100質量部に対して2質量%以下とする態様も好ましい。更には、塩基発生剤の含有量を、樹脂100質量部に対して1質量%以下とする態様も好ましく、0.5質量%以下とする態様もより好ましい。また、塩基発生剤の含有量を、樹脂100質量部に対して0.1質量%以下とする態様も好ましい。これらの態様において、塩基発生剤の含有量の下限は、0質量%であってもよい。
塩基発生剤の含有量は、特定樹脂から発生する塩基の種類及び量、現像液又は処理液に含まれる塩基の種類及び量、加熱条件等を考慮して決定することができる。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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、アミノ化合物等などが挙げられる。
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。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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、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における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。
本発明における樹脂組成物は、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における樹脂組成物の表面に偏在させてもよい。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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、本発明における樹脂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。
本発明における樹脂組成物は、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、本発明における樹脂組成物は、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。
本発明における樹脂組成物は、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、本発明における樹脂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。
本発明における樹脂組成物は、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、本発明における樹脂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。
本発明における樹脂組成物は、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、本発明における樹脂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。
本発明における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。
本発明における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。
上記分子量は、800以下であることが好ましく、600以下であることが更に好ましい。上記分子量の下限は特に限定されないが、例えば50以上とすることができる。
また、上記含有量は、30質量%以下であることが好ましく、10質量%以下であることが更に好ましい。
上記含有量の下限は特に限定されず、0質量%とすることもできる。
本発明の樹脂組成物は、環化樹脂の前駆体を含む樹脂組成物であって、下記測定条件1で熱質量測定をした場合の厚さの異なる3つの膜のうち、少なくとも1つの質量減少率が15質量%以下である。
測定条件1:
上記樹脂組成物をシリコン基板上に5μm、10μm、又は20μmの厚さでそれぞれ塗布し、100℃5分間乾燥した後に180℃、2時間の加熱により硬化物を得て、25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温した際の上記硬化物の質量減少率を測定する。
上記質量減少率は、下記式Aにより算出される
式A:質量減少率(%)={1-(300℃で加熱した後の膜の質量)/(25℃における膜の質量)}×100
上記効果が得られるメカニズムは不明であるが、以下のように推測される。
本発明の樹脂組成物は、上述の測定条件1で熱質量測定をした場合の厚さの異なる3つの膜のうち、少なくとも1つの質量減少率が15質量%以下である。
ここで、上記質量減少率が15質量%以下である場合、アウトガスの発生が抑制されたと推定されるため、硬化物と金属との密着性に優れると考えられる。
上記質量減少率は、実施例に記載の方法により測定される。
環化率は上述の方法により測定される。
環化率が上記範囲内である場合、未環化の部分を浸透パスとする金属層から硬化物への金属イオンの移行(マイグレーション)も抑制され、金属との密着性にさらに優れた硬化物が得られると考えられる。
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。
本発明の硬化物の詳細は、上述の本発明の硬化物の製造方法において得られる硬化物の詳細と同様であり、好ましい態様も同様である。
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。
ここで、上記積層体に含まれる上記硬化物からなる層が、いずれも本発明の硬化物からなる層である態様も、本発明の好ましい態様の1つである。
本発明の積層体は、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態様が好ましい。上記金属層は、上記金属層形成工程により形成されることが好ましい。
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。
また、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。
<ポリイミド前駆体樹脂(SA-1)の合成>
19.1g(61.2ミリモル)の4,4’-オキシジフタル酸二無水物と、12.3g(94ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、21.5g(272ミリモル)のピリジンと、80gのダイグライムとを混合し、25℃で撹拌した。続いて、2.18g(30.6ミリモル)のピロリジンを10gのダイグライムに溶解したものを30分かけて滴下したあと、60℃の温度で4時間撹拌し、25℃まで冷却した。続いて、上記反応液を-10℃まで冷却した後、塩化チオニル 15.3g(127ミリモル)を90分かけて滴下し、2時間撹拌した。続いて、4,4’-ビス(4-アミノフェノキシ)ビフェニル18.8g(51ミリモル)をNMP 100mL中に溶解させたものを、1時間かけて滴下したあと、2時間撹拌した。続いて、エタノール 9.0g(195ミリモル)を加え、混合物を2時間撹拌し、テトラヒドロフラン50mLを加え、3リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して取得し、4リットルの水の中で再度30分間撹拌したのち再び濾過し、得られたポリイミド前駆体樹脂を減圧下、45℃で24時間乾燥した。続いて、乾燥したポリイミド前駆体樹脂をテトラヒドロフラン300mLに溶解し、イオン交換樹脂50gを加え、6時間撹拌した後、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して取得し、45℃で2日間乾燥し、ポリイミド前駆体(SA-1)を得た。得られたポリイミド前駆体SA-1の重量平均分子量は23,100、数平均分子量は8,900であった。
SA-1の構造は下記式(SA-1)により表される構造であると推測される。
アミン(SA-1の合成におけるピロリジン)及びアルコール(SA-1の合成における2-ヒドロキシエチルメタクリレート)の種類並びにこれらのモル比を下記表に記載のように変更し、カルボン酸無水物(SA-1の合成における4,4’-オキシジフタル酸二無水物)及びジアミン(SA-1の合成における4,4’-ビス(4-アミノフェノキシ)ビフェニル)を適宜変更した以外は、SA-1と同様の方法で、SA-2~SA-4を合成した。
これらの樹脂の重量平均分子量(Mw)及び数平均分子量(Mn)はそれぞれ、下記表のMw、Mnの欄に記載した。
SA-2~SA-4の構造は、それぞれ、下記式(SA-2)~(SA-4)により表される構造であると推測される。下記式中、繰返し単位を表す括弧の添え字は各繰返し単位のモル比を表す。
14.8g(47.6ミリモル)の4,4’-オキシジフタル酸二無水物と、10.68g(81.9ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、16.7g(210ミリモル)のピリジンと、60gのダイグライムとを混合し、25℃で攪拌した。続いて、1.02g(14.3ミリモル)のピロリジンを10gのダイグライムに溶解したものを30分かけて滴下したあと、60℃の温度で4時間撹拌し、25℃まで冷却した。続いて、上記反応液を-10℃まで冷却した後、塩化チオニル 11.9(99ミリモル)を90分かけて滴下し、2時間撹拌した。続いて、4,4’-オキシジベンゾイルクロリド7.10g(23.8ミリモル)を添加し、30分撹拌した。続いて、4,4’-イソプロピリデンビス[(4-アミノフェノキシ)ベンゼン]25.0g(57ミリモル)をNMP 100mL中に溶解させたものを、1時間かけて滴下したあと、2時間撹拌した。続いて、エタノール 9.0g(195ミリモル)を加え、混合物を2時間撹拌し、テトラヒドロフラン50mLを加え、3リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して取得し、4リットルの水の中で再度30分間撹拌したのち再び濾過し、得られたポリイミド前駆体樹脂を減圧下、45℃で24時間乾燥した。続いて、乾燥したポリイミド前駆体樹脂をテトラヒドロフラン300mLに溶解し、イオン交換樹脂50gを加え、6時間撹拌した後、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して取得し、45℃で2日間乾燥し、ポリイミド前駆体(SA-5)を得た。得られたポリイミド前駆体SA-5の重量平均分子量は20,200、数平均分子量は8,100であった。
SA-5の構造は下記式(SA-5)により表される構造であると推測される。下記式中、繰返し単位を表す括弧の添え字は各繰返し単位のモル比を表す。
〔4,4’-オキシジフタル酸二無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-1:ラジカル重合性基を有するポリイミド前駆体)の合成〕
撹拌機、コンデンサー及び内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物 20.0g(65ミリモル)をジグリム 140mL中に懸濁させた。2-ヒドロキシエチルメタクリレート 16.8g(129ミリモル)、ヒドロキノン 0.05g、純水 0.05g及びピリジン 10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間撹拌した。次いで、混合物を-20℃まで冷却した後、塩化チオニル 16.1g(135.5ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、沈殿物を室温まで温め、2時間撹拌した後、ピリジン 9.7g(123ミリモル)及びN-メチルピロリドン(NMP) 25mLを添加し、透明溶液を得た。次いで、得られた透明溶液に、4,4’-ジアミノジフェニルエーテル 11.8g(58.7ミリモル)をNMP 100mL中に溶解させたものを、1時間かけて滴下により添加した。次いで、メタノール 5.6g(17.5ミリモル)と3,5-ジ-tert-ブチル-4-ヒドロキシトルエン 0.05gを加え、混合物を2時間撹拌した。次いで、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して取得し、4リットルの水の中で再度30分間撹拌したのち再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下、45℃で3日間乾燥しポリイミド前駆体(A-1)を得た。得られたポリイミド前駆体A-1の重量平均分子量は22,100、数平均分子量は9,400であった。
〔A-2:4,4’-オキシジフタル二酸無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-2:ラジカル重合性基を有するポリイミド前駆体)の合成〕
4,4’-オキシジフタル酸二無水物(ODPA)155.1gをセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)134.0g及びγ-ブチロラクトン400mlを加えた。室温下で撹拌しながら、ピリジン79.1gを加えることにより、反応混合物を得た。反応による発熱の終了後、室温まで放冷し、更に16時間静置した。
次に、氷冷下において、反応混合物に、ジシクロヘキシルカルボジイミド(DCC)206.3gをγ-ブチロラクトン180mlに溶解した溶液を、撹拌しながら40分かけて加えた。続いて、4,4’-ジアミノジフェニルエーテル93.0gをγ-ブチロラクトン350mlに懸濁した懸濁液を、撹拌しながら60分かけて加えた。更に室温で2時間撹拌した後、エチルアルコール30mlを加えて1時間撹拌した。その後、γ-ブチロラクトン400mlを加えた。反応混合物に生じた沈殿物を、ろ過により取得し、反応液を得た。
得られた反応液を3リットルのエチルアルコールに加えて、粗ポリマーからなる沈殿物を生成した。生成した粗ポリマーを濾取し、テトラヒドロフラン1.5リットルに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を28リットルの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾取した後に真空乾燥することにより、粉末状のポリマーA-2を得た。このポリマーA-2の重量平均分子量(Mw)を測定したところ、24,000であった。
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は、表の各欄の「添加量」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0.5μm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。
・SA-1~SA-5:上記で合成したSA-1~SA-5
・A-1~A-2:上記で合成したA-1~A-2
・SR-209:SR-209(サートマー社製)
・A-DPH(新中村化学工業社製、ジペンタエリスリトールヘキサアクリレート)
・C-1:IRGACURE OXE 01(BASF社製)
・C-2:IRGACURE OXE 02(BASF社製)
・C-3:下記構造の化合物
・H-1:N-フェニルジエタノールアミン(東京化成工業(株)製)
・DMSO:ジメチルスルホキシド
・GBL:γ-ブチロラクトン
・NMP:N-メチルピロリドン
表中、「DMSO/GBL」の記載はDMSOとGBLをDMSO:GBL=80:20の混合比(質量比)で混合したものを用いたことを示している。
・I-1:シクロヘキサノン
・I-2:ジメチルシクロヘキシルアミン5質量%シクロヘキサノン溶液
・J-1:PGMEA (プロピレングリコールモノメチルエーテルアセテート)
・J-2:ジメチルシクロヘキシルアミン10質量% PGMEA溶液
〔銅密着性の評価〕
上記ろ過後の各樹脂組成物及び比較用組成物を、それぞれ、銅基板上にスピンコート法(回転数:2000rpm(revolutions per minute))により層状に適用して、硬化性樹脂組成物層を形成した。得られた硬化性樹脂組成物層を適用した銅基板をホットプレート上で、100℃で5分間乾燥し、銅基板上に20μmの厚さの均一な硬化性樹脂組成物層とした。銅基板上の硬化性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで100μm四方のパターン形成用のフォトマスクを使用して露光し、その後表の「現像液」の欄に記載の現像液で60秒間現像して、表の「リンス液」の欄に記載のリンス液で30秒間リンスを行い、100μm四方形の樹脂層を得た。さらに、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表の「硬化条件」の「温度」の欄に記載の温度に達した後、この温度を2時間維持し樹脂膜2を得た。
銅基板上の100μm四方形の樹脂膜2に対して、25℃、65%相対湿度(RH)の環境下にて、ボンドテスター(XYZTEC社製、CondorSigma)を用いて、せん断力を測定した。せん断力が大きければ大きいほど密着力が大きく好ましい結果となる。評価は下記評価基準に従い行い、評価結果は表の「密着性」の欄に記載した。
-評価基準-
A:せん断力が35gfを超えた
B:せん断力が30gfを超えて35gf以下
C:せん断力が25gfを超えて30gf以下
D:せん断力が25gf以下
また、1gfは0.00980665Nである。
上記樹脂層及び銅基板を、表の「硬化条件」の欄に記載の温度で、2時間加熱した後に、175℃の恒温槽内で1000時間経過させた以外は、上述の金属密着性の評価における評価方法と同様の評価方法に従ってせん断力を測定し、加熱後の金属密着性の評価を行った。評価は下記の評価基準に従って行った。評価結果は表の「HTS後の密着性」の欄に記載した。せん断力が大きければ大きいほど硬化物の金属密着性(銅密着性)に優れるといえる。また、HTS後密着力の結果が優れていることから、長期間の経過後においても、硬化物と金属との間で剥がれが生じにくいといえる。
-評価基準-
A:せん断力が30gfを超えた。
B:せん断力が25gfを超えて30gf以下であった。
C:せん断力が20gfを超えて25gf以下であった。
D:せん断力が20gf以下であった。
また、1gfは0.00980665Nである。
各実施例及び比較例において調製した各樹脂組成物又は比較用組成物を、それぞれ、シリコンウエハ上にスピンコート法により適用し、樹脂組成物層を形成した。得られた樹脂組成物層を適用し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15μmの均一な厚さの樹脂組成物層を形成した。シリコンウェハ上の樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで全面露光し、全面露光後に樹脂組成物層を表の「現像液」の欄に記載の現像液で60秒間現像し、表の「リンス液」の欄に記載のリンス液を用いて30秒間リンスした。リンスした樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表の「硬化条件」の「温度」の欄に記載の温度で2時間加熱して、樹脂組成物層の硬化層(樹脂層)を得た。
上記硬化層における環化率及び質量減少率は上述の耐湿性評価における上記樹脂膜2の環化率及び質量減少率と同様であった。
得られた硬化層を温度121℃、湿度100%の高温高湿槽に250時間投入し、投入前と投入後の硬化層について、下記の薬液に下記の条件で浸漬し、膜べり量を測定した。
薬液:ジメチルスルホキシド(DMSO)と25質量%のテトラメチルアンモニウムヒドロキシド(TMAH)水溶液の90:10(質量比)の混合物
評価条件:薬液中に樹脂層を75℃で15分間浸漬して浸漬前後の膜厚を比較し、膜べり量(%)を算出した。膜厚は、エリプソメーター(Foothill社製KT-22)で塗布面10点において膜厚測定を実施し、その算術平均値として求めた。
評価は下記評価基準に従って行い、評価結果は表の「耐湿性」の欄に記載した。高温高湿槽に投入する前と投入した後の膜べり量の差(%)が少ないほど、耐湿性に優れるといえる。
高温高湿投入前後の膜べり量の差=A-B
A:高温高湿槽に投入する前の硬化層における、上記薬液に上記条件で浸漬した後の膜厚/浸漬する前の膜厚×100
B:高温高湿槽に投入した後の硬化層における、上記薬液に上記条件で浸漬した後の膜厚/浸漬する前の膜厚×100
-評価基準-
A:高温高湿投入前後の膜べり量の差が5%未満であった。
B:高温高湿投入前後の膜べり量の差が5%以上10%未満であった。
C:高温高湿投入前後の膜べり量の差が10%以上20%未満であった。
D:高温高湿投入前後の膜べり量の差が20%以上であった。
上記密着性評価で得られた上記樹脂膜2について、環化率(イミド化率)を測定し、表の「イミド化率(1)」の欄に記載した。
イミド化率は、下記方法により算出した。
上記樹脂膜2について、イミド構造由来の吸収ピークである1377cm-1付近のピーク強度P1を求め、樹脂膜2を350℃で1時間熱処理した後、再度、赤外吸収スペクトルを測定し、1377cm-1付近のピーク強度P2を求めた。
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を算出した。
イミド化率(%)=(ピーク強度P1/ピーク強度P2)×100
上記密着性評価で得られた上記樹脂膜2について、質量減少率を測定し、表の「質量減少率(1)」の欄に記載した。
上記樹脂膜2をアルミパンに1~5mg秤り入れ、NETZSCH Japan(株)製のTG-DTA2500を用いて下記条件で質量減少率(%)を測定した。
<測定条件>
窒素雰囲気下において、下記(1)~(4)の順に温度条件を変更して測定した。
(1)25℃から260℃まで、10℃/分の速度で昇温した。
(2)260℃で15分維持した。
(3)260℃から300℃まで、10℃/分の速度で昇温した。
(4)25℃以下に冷却した。
質量減少率(%)={1-(上記(1)における昇温を行う前の樹脂膜2の質量)/(上記(4)の冷却後の樹脂膜2の質量)}×100
各実施例及び比較例において、それぞれ、樹脂組成物又は比較用組成物をスピンコート法でシリコンウエハ上に厚さ5μm、10μm及び20μmでそれぞれ適用して計3種の厚さの樹脂組成物層を形成した。20μmの膜厚で塗布する場合、スピンコート法における回転数を2000rpmに設定して塗布した。10μmの膜厚で塗布する場合、組成物の固形分濃度を各組成物に含まれる溶剤(表に記載した溶剤)で29質量%まで希釈し、スピンコート法における回転数を1500rpmに設定して塗布した。5μmの膜厚で塗布する場合、組成物の固形分濃度を各組成物に含まれる溶剤(表に記載した溶剤)で29質量%まで希釈し、スピンコート法における回転数を3000rpmに設定して塗布した。得られた樹脂組成物層適用したシリコンウエハを、それぞれ、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樹脂組成物層を形成した。
上記樹脂組成物層を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、180℃に達した後、この温度を2時間維持し硬化物を得た。
上記硬化物を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。
上記硬化物をアルミパンに1~5mg秤り入れ、NETZSCH Japan(株)製のTG-DTA2500を用いて、上述の質量減少率の測定(1)と同様の条件で質量減少率(%)を測定した。
上記3種の厚さの樹脂組成物層から得られた硬化物について、それぞれ、下記式により質量減少率を算出し、下記式Aにより表の「質量減少率」の欄に記載した。
式A:質量減少率(%)={1-(300℃で加熱した後の膜の質量)/(25℃における膜の質量)}×100
上記3種の厚さの樹脂組成物層から得られた硬化物の質量減少率のうち、最小値を表の「質量減少率(2)」の欄に記載した。「質量減少率(2)」の欄に「-」と記載された例においては、質量減少率の測定(2)の評価を行わなかった。また、質量減少率が最小となった硬化物のイミド化率は、表の「イミド化率(2)」の欄に記載した。上記イミド化率は、上述の「イミド化率(1)」と同様の方法により測定した。
比較例1~4に係る硬化物の製造方法は、得られる硬化物のイミド化率が95%未満であり、また、比較例1~5に係る樹脂組成物は、測定条件1における質量減少率が15%を超える。
このような比較例1~5に係る硬化物の製造方法により得られる硬化物、及び、比較用組成物からなる硬化物は、金属との密着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4分間乾燥し、膜厚20μmの樹脂組成物層を形成した後、ステッパー((株)ニコン製、NSR1505 i6)を用いて露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が10μmであるバイナリマスク)を介して、波長365nmで行った。露光後、100℃で4分間加熱した。上記加熱後、シクロヘキサノン(I-1)で2分間現像し、PGMEA(J-1)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、180℃に達した後、180℃で2時間維持して、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 (24)
- 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、及び、
前記膜を180℃以下の加熱温度で加熱する加熱工程を含む硬化物の製造方法であって、
前記加熱工程後の膜を25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温した際の下記式Aで表される質量減少率が、15%以下であり、
得られる硬化物における、前記環化樹脂の前駆体から得られる環化樹脂の環化率が95%以上である
硬化物の製造方法。
式A:質量減少率(%)={1-(300℃で加熱した後の膜の質量)/(25℃における膜の質量)}×100 - 前記加熱工程における加熱温度が150℃を超える、請求項1に記載の硬化物の製造方法。
- 前記質量減少率が10%以下である、請求項1又は2に記載の硬化物の製造方法。
- 前記質量減少率が5%以下である、請求項1~3のいずれか1項に記載の硬化物の製造方法。
- 前記環化率が98%以上である、請求項1~4のいずれか1項に記載の硬化物の製造方法。
- 前記加熱工程後の膜がポリイミド膜である、請求項1~5のいずれか1項に記載の硬化物の製造方法。
- 前記膜形成工程と、前記加熱工程との間に、膜を選択的に露光する露光工程を更に含む、請求項1~6のいずれか1項に記載の硬化物の製造方法。
- 前記露光工程と、前記加熱工程との間に、現像液により前記露光後の膜を現像してパターンを形成する現像工程を更に含む、請求項7に記載の硬化物の製造方法。
- 前記現像液が、有機溶剤を含む、請求項8に記載の硬化物の製造方法。
- 前記現像工程が、ネガ型のパターンを形成する工程である、請求項8又は9に記載の硬化物の製造方法。
- 前記現像液が塩基を含む、請求項8~10のいずれか1項に記載の硬化物の製造方法。
- 前記現像工程と、前記加熱工程の間に、塩基を含む処理液と前記パターンとを接触させる処理工程を含む、請求項8~11のいずれか1項に記載の硬化物の製造方法。
- 前記樹脂組成物が、感光剤を含む、請求項1~12のいずれか1項に記載の硬化物の製造方法。
- 前記樹脂組成物が、溶剤を含み、前記環化樹脂の前駆体の含有量が、樹脂組成物の全固形分に対して70質量%以上である、請求項1~13のいずれか1項に記載の硬化物の製造方法。
- 前記樹脂組成物が、1気圧における沸点が270℃以上である重合性化合物を含む、請求項1~14のいずれか1項に記載の硬化物の製造方法。
- 前記1気圧における沸点が270℃以上である重合性化合物が、(メタ)アクリレート基を3つ以上有する化合物である、請求項15に記載の硬化物の製造方法。
- 分子量が1000以下である成分であって、溶剤とは異なる成分の含有量が、樹脂組成物の全固形分に対して30質量%以下である、請求項1~16のいずれか1項に記載の硬化物の製造方法。
- 前記環化樹脂の前駆体が、下記式(1-1)で表される繰り返し単位及び下記式(1-2)で表される繰り返し単位の少なくとも一方を有する樹脂を含む、
請求項1~17のいずれか1項に記載の硬化物の製造方法。
- 請求項1~18のいずれか1項に記載の硬化物の製造方法を複数回繰り返すことを含む、積層体の製造方法。
- 請求項1~18のいずれか1項に記載の硬化物の製造方法、又は、請求項19に記載の積層体の製造方法を含む、半導体デバイスの製造方法。
- 環化樹脂の前駆体を含む樹脂組成物であって、
下記測定条件1で熱質量測定をした場合の厚さの異なる3つの膜のうち、少なくとも1つの質量減少率が15質量%以下である
樹脂組成物;
測定条件1:
前記樹脂組成物をシリコン基板上に5μm、10μm、又は20μmの厚さでそれぞれ塗布し、100℃5分間乾燥した後に180℃、2時間の加熱により硬化物を得て、25℃に戻した前記硬化物を25℃から260℃まで10℃/分の速度で昇温し、260℃で15分維持し、260℃から300℃まで10℃/分の速度で昇温した際の前記硬化物の質量減少率を測定する。
前記質量減少率は、下記式Aにより算出される
式A:質量減少率(%)={1-(300℃で加熱した後の膜の質量)/(25℃における膜の質量)}×100 - 請求項21に記載の樹脂組成物を硬化してなる硬化物。
- 環化樹脂の前駆体を含む樹脂組成物を硬化してなる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のうち少なくとも1層が請求項22に記載の硬化物からなる層である
積層体。 - 請求項22に記載の硬化物又は請求項23に記載の積層体を含む、
半導体デバイス。
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WO2016194769A1 (ja) * | 2015-05-29 | 2016-12-08 | 富士フイルム株式会社 | ポリイミド前駆体組成物、感光性樹脂組成物、硬化膜、硬化膜の製造方法、半導体デバイスおよびポリイミド前駆体組成物の製造方法 |
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WO2020071437A1 (ja) * | 2018-10-03 | 2020-04-09 | 日立化成デュポンマイクロシステムズ株式会社 | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
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WO2018151195A1 (ja) * | 2017-02-20 | 2018-08-23 | 富士フイルム株式会社 | 感光性樹脂組成物、複素環含有ポリマー前駆体、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス |
WO2020071437A1 (ja) * | 2018-10-03 | 2020-04-09 | 日立化成デュポンマイクロシステムズ株式会社 | 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 |
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