WO2022050041A1 - Cured product production method, laminate production method, and electronic device production method - Google Patents
Cured product production method, laminate production method, and electronic device production method Download PDFInfo
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- WO2022050041A1 WO2022050041A1 PCT/JP2021/030027 JP2021030027W WO2022050041A1 WO 2022050041 A1 WO2022050041 A1 WO 2022050041A1 JP 2021030027 W JP2021030027 W JP 2021030027W WO 2022050041 A1 WO2022050041 A1 WO 2022050041A1
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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
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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
- G03F7/028—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
- G03F7/038—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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/02—Bonding areas ; Manufacturing methods related thereto
- H01L24/03—Manufacturing methods
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/03—Manufacturing methods
- H01L2224/0347—Manufacturing methods using a lift-off mask
- H01L2224/0348—Permanent masks, i.e. masks left in the finished device, e.g. passivation layers
Definitions
- the present invention relates to a method for producing a cured product, a photosensitive resin composition, a method for producing a laminate, and a method for producing an electronic device.
- Resins such as polyimide are applied to various applications because they have excellent heat resistance and insulating properties.
- the application is not particularly limited, and examples thereof include semiconductor devices for mounting, such as using a pattern containing these resins as a material for an insulating film or a sealing material, or as a protective film.
- patterns containing these resins are also used as base films and coverlays for flexible substrates.
- a resin such as polyimide is used in the form of a photosensitive resin composition containing a polyimide precursor.
- a photosensitive resin composition containing a polyimide precursor.
- a cured product in which the polyimide precursor is imidized is used as a base material.
- the photosensitive resin composition can be applied by a known coating method or the like, and a fine pattern, a pattern having a complicated shape, or the like can be formed by development. It can be said that it is excellent in sex.
- industrial application development of a method for manufacturing a cured product using a photosensitive resin composition containing a polyimide precursor is increasing. It is expected.
- Patent Document 1 describes at least one selected from the group consisting of (a) basic compounds and (b) amides, ketones, esters, lactones, ethers, halogenated hydrocarbons and hydrocarbons.
- a developer for a photosensitive polyimide precursor containing one kind of organic solvent is described.
- Patent Document 2 describes (A) a basic compound and / or a basic aqueous solution, (B) an alcohol compound, (C) N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, At least one solvent selected from the group consisting of dimethyl sulfoxide, hexamethylenephosphoric triamide, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-acetyl- ⁇ -caprolactam, tetramethylene sulfone, as well as (D) is composed of a mixed solvent of a ketone compound, (A) is 2 to 15 parts by weight, (B) is 25 to 60 parts by weight, (C) is 25 to 60 parts by weight, and (D) is 2 to 15 parts by weight.
- a photosensitive resin composition containing a polyimide precursor is applied to a substrate to form a film, the film is exposed and developed, and then the precursor is imidized by heating to produce a cured product.
- the imidization improves the mechanical properties of the film (eg, elongation at break) and improves the reliability of the module.
- it is desired to provide a method for producing the cured product which can obtain a cured product having excellent elongation at break even when cured at a low temperature.
- the cured product is used as an interlayer insulating film for the rewiring layer.
- the substrate in which the insulating film is used is increasing in area from a wafer size of 8 inches to a size of 12 inches and a panel level.
- the number of layers to be laminated is gradually increasing from 1 layer to 2 layers, 3 layers, 4 layers and 5 layers.
- the above-mentioned heating is performed at a low temperature (for example, 240 ° C. or lower, preferably 200 ° C. or lower). , More preferably at 180 ° C. or lower).
- a low temperature for example, 240 ° C. or lower, preferably 200 ° C. or lower.
- the above-mentioned heating is performed at a low temperature, the above-mentioned imidization does not proceed sufficiently, and the breaking elongation of the above-mentioned film may decrease.
- the present invention relates to a method for producing a cured product that can obtain a cured product having excellent elongation at break even when cured at a low temperature, a method for producing a laminate including the method for producing the cured product, and the cured product. It is an object of the present invention to provide a manufacturing method or a manufacturing method of an electronic device including the manufacturing method of the above-mentioned laminate.
- An exposure process that selectively exposes the film A developing step of developing a film after exposure to form a pattern with a developing solution containing at least one compound selected from the group consisting of bases and base generators, and Including a heating step of heating the pattern obtained by the above development.
- the content of water with respect to the total mass of the developer is 50% by mass or less.
- a 1 and A 2 independently represent an oxygen atom or -NH-
- R 113 and R 114 independently represent a monovalent organic group
- R 115 is a tetravalent organic.
- the group represents a group
- R 111 represents a divalent organic group.
- ⁇ 4> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 3>, wherein the heating temperature in the heating step is 120 to 230 ° C.
- ⁇ 5> The cured product according to any one of ⁇ 1> to ⁇ 4>, wherein the developing step is a step of supplying the developing solution to the exposed film by a shower or continuously supplying the developing solution. Manufacturing method.
- ⁇ 6> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 5>, wherein the development in the development step is negative type development.
- ⁇ 8> The method for producing a laminate according to ⁇ 7>, further comprising a metal layer forming step of forming a metal layer on the cured product between the methods for producing the cured product which is performed a plurality of times.
- a method for manufacturing an electronic device which comprises the method for manufacturing a cured product according to any one of ⁇ 1> to ⁇ 6>, or the method for manufacturing a laminate according to ⁇ 7> or ⁇ 8>.
- a method for producing a cured product that can obtain a cured product having excellent elongation at break even when cured at a low temperature, a method for producing a laminate including the method for producing the cured product, and the above-mentioned curing.
- a method for manufacturing an electronic device including a method for manufacturing a product or a method for manufacturing the above-mentioned laminate is provided.
- the present invention is not limited to the specified embodiments.
- the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
- the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
- the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacrylic", or.
- Any, and “(meth) acryloyl” means both “acryloyl” and “methacrylic”, or either.
- Me in the structural formula represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- the total solid content means the total mass of all the components of the composition excluding the solvent.
- the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified.
- GPC gel permeation chromatography
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns.
- Super HZ4000, TSKgel Super HZ3000, and TSKgel It can be obtained by connecting Super HZ2000 (all manufactured by Tosoh Corporation) in series.
- the molecular weights shall be measured using THF (tetrahydrofuran) as an eluent.
- NMP N-methyl-2-pyrrolidone
- the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
- UV rays ultraviolet rays
- a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
- the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper”. And the opposite direction is called "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
- the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
- the content of each component in the composition means the total content of all the compounds corresponding to the component.
- the temperature is 23 ° C.
- the atmospheric pressure is 101,325 Pa (1 atmospheric pressure)
- the relative humidity is 50% RH.
- a combination of preferred embodiments is a more preferred embodiment.
- the method for producing a cured product of the present invention has a photosensitive resin composition containing a polyimide precursor having a repeating unit represented by the following formula (2) (hereinafter, also referred to as "specific resin") and a photopolymerization initiator.
- the development step of developing the film after the exposure to form a pattern and the heating step of heating the pattern obtained by the development are included, and the content of water with respect to the total mass of the developer is 50% by mass or less. Is.
- a 1 and A 2 independently represent an oxygen atom or -NH-
- R 113 and R 114 independently represent a monovalent organic group
- R 115 is a tetravalent organic.
- the group represents a group
- R 111 represents a divalent organic group.
- a cured product having excellent elongation at break can be obtained even when cured at a low temperature.
- the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
- a developer containing at least one compound selected from the group consisting of a base and a base generator is used as the developer.
- at least one of the base and the base generator contained in the developer permeates the pattern obtained by the development at the time of development. Due to the action of at least one of the base or the base generator transferred from the developer to the pattern, the polyimide precursor described above is likely to be imidized even at a low temperature, and a significant decrease in temperature can be realized at the time of heating. It is presumed.
- Patent Documents 1 and 2 a polyimide precursor having a repeating unit represented by the above formula (2) and a photosensitive resin composition containing a photopolymerization initiator are used, and a base and a base are generated. There is no description of developing the post-exposure film to form a pattern with a developer containing at least one compound selected from the group consisting of agents.
- a developer containing at least one compound selected from the group consisting of agents Thereinafter, the method for producing a cured product of the present invention will be described in detail.
- the method for producing a cured product of the present invention includes a film forming step of applying a photosensitive resin composition onto a substrate to form a film. Details of the photosensitive resin composition used in the present invention (hereinafter, also simply referred to as “resin composition”) will be described later.
- the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, Any of a metal base material such as a magnetic film, a reflective film, Ni, Cu, Cr, Fe (for example, a base material formed of metal, or a base material in which a metal layer is formed by, for example, plating or thin film deposition). (May be good), paper, SOG (Spin On Glass), TFT (thin film film) array base material, mold base material, electrode plate of plasma display panel (PDP), and the like, and are not particularly limited.
- semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film
- a metal base material such as a magnetic film, a reflective film, Ni, Cu, Cr, Fe (
- a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable. Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
- the shape of the base material is not particularly limited, and may be circular or rectangular. The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
- a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used as the base material.
- a resin composition when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.
- Coating is preferable as a means for applying the resin composition of the present invention on a substrate.
- the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
- An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity.
- the method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained.
- the coating method can be appropriately selected depending on the shape of the substrate.
- a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable.
- the method, the inkjet method and the like are preferable.
- the spin coating method for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
- the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
- a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
- EBR edge bead rinse
- a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
- the film may be subjected to a step (drying step) of drying the film (layer) formed to remove the solvent after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
- the drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure.
- the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.
- the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed by the film forming step.
- Selective exposure means exposing a part of the film.
- an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
- the exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 . Is more preferable.
- the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
- the exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength).
- the resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays.
- the exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.
- the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
- the post-exposure heating step can be performed after the exposure step and before the developing step.
- the heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
- the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
- the heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature. Further, the heating rate may be appropriately changed during heating.
- the heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used. Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.
- the method for producing a cured product of the present invention includes a developing step of developing a film after exposure with a developing solution containing at least one compound selected from the group consisting of a base and a base generator to form a pattern. ..
- a developing solution containing at least one compound selected from the group consisting of a base and a base generator to form a pattern.
- the development in which the non-exposed part is removed by the developing process is called negative type development
- the development in which the exposed part is removed by the developing process is called positive type development.
- the development in the development step included in the method for producing a cured product of the present invention is preferably negative type development.
- the developer used in the method for producing a cured product of the present invention is a developer containing at least one compound selected from the group consisting of a base and a base generator, and is water with respect to the total mass of the developer.
- the content is 50% by mass or less.
- a developer containing at least one of a base and a base generator is used, as a result, a cured product having excellent elongation at break after heating is obtained. It is presumed that this is because the base in the developer immersed in the pattern promotes imidization in the heating step.
- the content of the water is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 2% by mass or less.
- the lower limit of the water content is not particularly limited and may be 0% by mass.
- the developer preferably contains at least a base.
- a base contained in the developing solution an organic base is preferable from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated).
- a base having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide and the like are preferable, but in order to promote the imidization reaction, a primary amine is preferable.
- the base a base that does not easily remain in the cured film (obtained cured product) is preferable from the viewpoint of mechanical properties (break elongation) of the cured product, and from the viewpoint of promoting imidization, it is before heating due to vaporization or the like. It is preferable that the residual amount does not easily decrease. Therefore, the boiling point of the base is preferably 30 ° C. to 350 ° C., more preferably 80 ° C.
- the boiling point of the base is preferably higher than the temperature obtained by subtracting 20 ° C. from the boiling point of the organic solvent contained in the developing solution, and more preferably higher than the boiling point of the organic solvent contained in the developing solution.
- the base used has a boiling point of 80 ° C. or higher, more preferably 100 ° C. or higher.
- the base contained in the developing solution include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, and N-methylaniline.
- 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, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N, N-diethyl Ethylenediamine, N, N, N', N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis (2-methoxyethyl) amine, piperidine, di
- the content of the base with respect to the total mass of the developing solution is preferably 0.01 to 100% by mass, more preferably 0.05 to 20% by mass, and 0.1 to 10% by mass. % Is more preferable.
- the base is not a liquid at 10 to 30 ° C.
- the content of the base is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass.
- the base may be used alone or in combination of two or more. When two or more kinds of bases are used in combination in a developing solution, the total content thereof is preferably within the above range.
- the developer may contain a base generator.
- the base generator include a photobase generator or a thermobase generator, and a thermobase generator is preferable.
- the photobase generator or the thermobase generator for example, the photobase generator or the thermobase generator described as a component contained in the photosensitive resin composition described later can be used without particular limitation.
- the content of the base generator with respect to the total mass of the developing solution is preferably 0.1 to 50% by mass, more preferably 0.2 to 20% by mass, and 0. It is more preferably 3 to 10% by mass.
- the base generator may be used alone or in combination of two or more. When two or more kinds of base generators are used in combination in a developing solution, the total content thereof is preferably within the above range.
- the developer preferably contains 50% by mass or more of the organic solvent, and more preferably 80% by mass or more, based on the total mass of the developer.
- the upper limit of the content of the organic solvent is not particularly limited, but is preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and preferably 99.5% by mass or less. It is more preferably 99.0% by mass or less, and particularly preferably 99.0% by mass or less.
- the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
- the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
- organic solvent examples include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
- alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl propionate, etc.
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- dimethyl sulfoxide as sulfoxides
- alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene glycol, etc., and amides.
- Preferred examples thereof include N-methylpyrrolidone, N-ethylpyrrolidone and dimethylformamide.
- the above-mentioned base for example, an organic base
- the above-mentioned base can be used as a solvent and a base.
- the above-mentioned organic solvent can be used alone or in combination of two or more.
- cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone and cyclohexanone are particularly preferable, and cyclopentanone, ⁇ -butyrolactone and dimethyl sulfoxide are more preferable, and cyclopentanone is most preferable.
- the developer may further contain other components.
- other components include known surfactants and known defoaming agents.
- the method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle.
- the type of nozzle is not particularly limited, and examples thereof include straight nozzles and shower nozzles, and examples of the shower nozzles include spray nozzles and the like.
- the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a shower nozzle is preferable, and the developing solution to the image area is supplied. From the viewpoint of permeability, the method of supplying with a shower nozzle is more preferable. Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
- the method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate.
- a process of vibrating with a sound wave or the like and a process of combining them can be adopted.
- the developing step is preferably a step of supplying the developing solution to the exposed film by a shower or continuously supplying the developing solution.
- the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
- the pattern may be further washed (rinsed) with the rinsing solution. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
- a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
- the rinsing solution for example, a solvent different from the solvent contained in the developing solution (for example, an organic solvent different from the organic solvent contained in the developing solution) can be used. Further, the solvent contained in the developing solution may be used as the rinsing solution.
- the rinsing liquid may further contain water in addition to the above solvent. Further, the rinsing solution may further contain at least one compound selected from the group consisting of the base and the base generator contained in the above-mentioned developer.
- the rinsing time is not particularly limited, but may be, for example, 5 seconds to 5 minutes, preferably 10 seconds to 2 minutes.
- the pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) is subjected to a heating step of heating the pattern obtained by the above-mentioned development. That is, the method for producing a cured product of the present invention includes a heating step of heating the pattern obtained by the developing step. Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step. In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as polyimide.
- the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 160 to 250 ° C, and even more preferably 150 to 230 ° C.
- the heating step promotes imidization of the polyimide precursor in the pattern by the action of at least one compound selected from the group consisting of the base and the base generated from the base generator by heating. It is preferably a process.
- the heating in the heating step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature.
- the temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min.
- the temperature at the start of heating it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. °C / sec is more preferable.
- the temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and even more preferably 25 ° C to 120 ° C.
- the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
- the resin composition of the present invention when applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, for example, from the boiling point of the solvent contained in the resin composition of the present invention.
- the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
- the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher, from the viewpoint of adhesion between layers of the pattern. It is preferably 120 ° C. or higher, and particularly preferably 120 ° C. or higher.
- the upper limit of the heating temperature is preferably 350 ° C. or lower, more preferably 250 ° C. or lower, further preferably 230 ° C. or lower, and particularly preferably 200 ° C. or lower. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
- Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. It is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step.
- the pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
- the pretreatment may be performed in two or more steps, for example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
- the heating step is preferably carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under reduced pressure in order to prevent decomposition of the specific resin.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
- the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
- the method for producing a cured product of the present invention may further include a post-development exposure step for exposing the pattern after the developing step.
- a post-development exposure step for example, a photobase generator or the like, which is a photosensitive compound described later, is exposed to light, cyclization of the polyimide precursor proceeds, and a cured pattern is obtained.
- the post-development exposure step at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
- the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity.
- the post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.
- the pattern obtained in the developing step may be subjected to the metal layer forming step of forming the metal layer on the pattern. That is, it is preferable that the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one subjected to a heating step).
- metal layer existing metal species can be used without particular limitation, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.
- the method for forming the metal layer is not particularly limited, and an existing method can be applied.
- the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. No. 7,788,181B2, US Pat. No. 9,177,926B2 are used. can do.
- photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered.
- a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.
- Preferred embodiments of plating include electrolytic plating using a copper sulfate or copper cyanide plating solution.
- the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m in the thickest portion.
- Examples of the method for producing a cured product of the present invention or the applicable field of the cured product of the present invention include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
- Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd.
- the method for producing a cured product of the present invention, or the cured product of the present invention is used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, protective lacquer and dielectric in electronics, especially microelectronics. It can also be used for layer production and the like.
- the laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
- the laminated body of the present invention is a laminated body including two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
- the two or more layers made of the cured product contained in the laminated body at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.
- the method for producing 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 a plurality of times.
- the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product.
- the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times.
- the preferred embodiment of the metal layer forming step is as described above.
- a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention.
- the resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition.
- the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
- the method for producing a laminated body of the present invention preferably includes a laminating step.
- the laminating step is a process of (a) film forming step (layer forming step), (b) exposure step, (c) developing step, and (d) heating step again on the surface of the pattern (resin layer) or metal layer. It is a series of steps including performing in this order. However, it may be an embodiment in which the film forming step (a) and the heating step (d) are repeated. Further, (d) the heating step may be followed by (e) a metal layer forming step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.
- the surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step.
- Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
- the laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
- a structure having two or more and 20 or less resin layers such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
- the composition, shape, film thickness, etc. of each of the above layers may be the same or different.
- a cured product (resin layer) of the resin composition of the present invention so as to further cover the metal layer after the metal layer is provided.
- a film forming step an exposure step, (c) a developing step, (d) a heating step (e) a metal layer forming step are repeated in this order, or (a) film forming.
- the step, (d) heating step, and (e) 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 surface activating at least a part of the metal layer and the resin composition layer.
- the surface activation treatment step is usually performed after the metal layer forming step, but after the development step, the surface activation treatment step may be performed on the resin composition layer, and then the metal layer forming step may be performed.
- the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the exposed resin composition layer, or on the metal layer and the exposed resin composition layer. For both, you may go to at least part of each.
- the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region forming the resin composition layer on the surface of the metal layer.
- the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment.
- the resin composition layer when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
- Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2 .
- the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , and most preferably 10,000 to 50,000 J / m 2 .
- the present invention also discloses a method for producing a cured product of the present invention, or a method for producing an electronic device including a method for producing a laminate of the present invention.
- the electronic device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
- the photosensitive resin composition is a photosensitive resin composition used in the method for producing a cured product of the present invention, the method for producing a laminate of the present invention, or the method for producing an electronic device of the present invention.
- the photosensitive resin composition of the present invention contains a polyimide precursor having a repeating unit represented by the formula (2) and a photopolymerization initiator.
- the photosensitive resin composition contains a polyimide precursor (specific resin) having a repeating unit represented by the formula (2). Further, the specific resin preferably has a radically polymerizable group. When the specific resin has a radically polymerizable group, the photosensitive resin composition preferably contains a photoradical polymerization initiator described later as a photopolymerization initiator, and also contains a photoradical polymerization initiator described below and is described later. It is more preferable to contain a radical cross-linking agent, and further preferably to contain a photoradical polymerization initiator described later, a radical cross-linking agent described later, and a sensitizer described later.
- the specific resin may have a polar conversion group such as an acid-decomposable group.
- the photosensitive resin composition preferably contains a photoacid generator described later. From such a photosensitive resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.
- the polyimide precursor used in the present invention contains a repeating unit represented by the following formula (2).
- a 1 and A 2 independently represent an oxygen atom or -NH-
- R 111 represents a divalent organic group
- R 115 represents a tetravalent organic group
- R 113 and R 114 each independently represent a monovalent organic group.
- a 1 and A 2 in the formula (2) independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.
- R 111 in the formula (2) represents a divalent organic group.
- the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified.
- a cyclic aliphatic group having 3 to 20, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
- the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a group containing.
- Preferred embodiments of the present invention are exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably groups represented by -Ar-L-Ar-.
- Ar is an aromatic group independently
- L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be single-bonded or substituted with a fluorine atom, -O-, -CO. -, -S-, -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
- R 111 is preferably derived from diamine.
- the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable.
- the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a containing group.
- groups containing aromatic groups include:
- O)-, -S-, -SO 2- , -NHCO-, or a group selected from a combination thereof is preferable, and a single bond or a group having 1 to 3 carbon atoms which may be substituted with a fluorine atom may be used.
- * represents a binding site with another structure.
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-,1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl;
- diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.
- a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.
- R 111 is preferably represented by ⁇ Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film.
- Ar is an aromatic group independently
- L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
- Ar is preferably a phenylene group
- L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO2- . ..
- the aliphatic hydrocarbon group here is preferably an alkylene group.
- R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance.
- a divalent organic group represented by the formula (61) is more preferable.
- Equation (51) In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or trifluoro. It is a methyl group, and each of * independently represents a bonding site with a nitrogen atom in the formula (2).
- the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
- R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is an independent binding site with a nitrogen atom in formula (2). show.
- Examples of the diamine giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and 2,2'-bis. (Fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
- R 115 in the formula (2) represents a tetravalent organic group.
- a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
- * independently represents a binding site with another structure.
- R 112 is a single bond or divalent linking group, which may be replaced with a single bond or a fluorine atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, —O—, It is preferably a group selected from -CO-, -S-, -SO 2- , and -NHCO-, and combinations thereof, and has a single bond or the number of carbon atoms which may be substituted with a fluorine atom. More preferably, it is a group selected from 1 to 3 alkylene groups, -O-, -CO-, -S- and -SO 2- , and -CH 2- , -C (CF 3 ) 2 -,-. It is more preferably a divalent group selected from the group consisting of C (CH 3 ) 2- , -O-, -CO-, -S- and -SO 2- .
- R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride.
- the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types as a structure corresponding to R 115 .
- 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 the formula (2), and the preferred range is also the same.
- tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-.
- PMDA pyromellitic acid dianhydride
- 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride 3,3', 4,4'-.
- tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
- R 113 and R 114 in the formula (2) each independently represent a monovalent organic group.
- the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Further, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that 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.
- a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like.
- the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group and an amino group. Be done.
- a group having an ethylenically unsaturated bond is preferable.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to the vinyl group (for example, a vinylphenyl group), and a (meth) acrylamide group.
- R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.
- * represents a binding site with another structure.
- R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- , a cycloalkylene group or a polyalkyleneoxy group.
- R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, alkylene group such as ethylene group, propylene group, -CH 2 CH (OH) CH 2- , cyclohexyl group, polyalkylene An oxy group is more preferable, and an alkylene group such as an ethylene group and a propylene group, or a polyalkylene oxy group is further preferable.
- alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group,
- the polyalkyleneoxy group refers to a group to which two or more alkyleneoxy groups are directly bonded.
- the alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
- R 113 and R 114 may be a polar conversion group such as an acid-degradable group.
- the acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group.
- a tertiary alkyl ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity.
- the acid-degradable group examples include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl.
- examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
- the polyimide precursor has a fluorine atom in its structure.
- the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine an embodiment using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like can be mentioned.
- the repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude. Equation (2-A) In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group, at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.
- a 1 , A 2 , R 111 , R 113 , and R 114 are independently synonymous with A 1 , A 2 , R 111 , R 113 , and R 114 in the formula (2), and the preferred ranges are also the same. .. R 112 has the same meaning as R 112 in the formula (5), and the preferred range is also the same.
- the polyimide precursor may contain one kind of repeating unit represented by the formula (2), but may contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).
- the content of the repeating unit represented by the formula (2) is 50 mol% or more of all the repeating units.
- the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
- the upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal may be the repeating unit represented by the formula (2).
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
- the number average molecular weight (Mn) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 8,000 to 20,000.
- the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.8 or more, more preferably 2.0 or more, and further preferably 2.2 or more.
- the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
- the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
- the resin composition contains a plurality of types of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion of at least one type of polyimide precursor are in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyimide precursors as one resin are within the above ranges.
- the polyimide precursor and the like can be, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature, or reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature to obtain a polyamic acid, and a condensing agent or an alkylating agent.
- the remaining dicarboxylic acid can be obtained by acid-halogenizing it with a halogenating agent and reacting it with a diamine.
- a method in which a diester is obtained from tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated with a halogenating agent and reacted with a diamine is more preferable.
- Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples thereof include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
- Examples of the alkylating agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethylacetal, N, N-dialkylformamidedialkylacetal, trimethyl orthoformate, triethyl orthoformate and the like.
- halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
- an organic solvent in the reaction.
- the organic solvent may be one kind or two or more kinds.
- the organic solvent can be appropriately determined depending on the raw material, but is pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone and the like. Is exemplified.
- the basic compound may be one kind or two or more kinds.
- the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, N, N-dimethyl-4-amino. Examples thereof include pyridine and the like.
- -End sealant- In the method of producing a polyimide precursor or the like, in order to further improve the storage stability, it is necessary to seal the carboxylic acid anhydride, the acid anhydride derivative, or the amino group remaining at the resin terminal of the polyimide precursor or the like. be.
- examples of the terminal encapsulant include monoalcohol, phenol, thiol, thiophenol, monoamine, etc., and are reactive and stable in the film. From the viewpoint of properties, it is more preferable to use monoalcohol, phenols and monoamines.
- Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and flufuryl alcohol, and isopropanol.
- Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and hydroxystyrene.
- Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-.
- Aminonaphthalene 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -Aminobenzene sulfonic acid, 3-amino-4,6-di
- encapsulants for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, anhydrous sulfonic acids, sulfonic acid carboxylic acid anhydrides and the like, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable.
- Preferred compounds for carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornen-2,3-dicarboxylic acid anhydride and the like.
- Preferred compounds for the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride and 1-adamantancarbonyl chloride.
- Heptafluorobutyryl chloride stearate chloride, benzoyl chloride, and the like.
- a step of precipitating a solid may be included in the production of a polyimide precursor or the like. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution was filtered off as necessary, and then obtained in a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof. By adding the polymer component and precipitating the polymer component, it is precipitated as a solid, and by drying, a polyimide precursor or the like can be obtained. In order to improve the degree of purification, operations such as redissolution, reprecipitation and drying of the polyimide precursor may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.
- the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the resin composition. More preferably, it is more preferably 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the resin composition. % Or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
- the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the resin composition of the present invention contains at least two kinds of resins.
- the resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but the specific resin may be contained. It is preferable to include two or more kinds.
- the resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimides which are polyimide precursors and have different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to include a precursor.
- the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
- Other resins include polyamide-imide, polyamide-imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth) acrylic resins, (meth) acrylamide resins, urethane resins, butyral resins, styryl. Examples thereof include resins, polyether resins, and polyester resins.
- a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
- a high polymerizable base value having a weight average molecular weight of 50,000 or less for example, the molar amount of the polymerizable group contained in 1 g of the resin. (1 ⁇ 10 -3 mol / g or more)
- the content of the other resin may be more than 0% by mass, but is 0.1% by mass or more, based on the total solid content of the resin composition. It is preferably 0.5% by mass or more, and more preferably 0.5% by mass or more. Further, the content of other resins in the resin composition of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the resin composition. It is more preferably mass% or less.
- the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
- the photosensitive resin composition contains a photopolymerization initiator.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators.
- a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
- it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
- the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). Is preferable.
- the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- a known compound can be arbitrarily used.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like.
- paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification. Further, paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No.
- ketone compound for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification.
- Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also preferably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the contents thereof are described in the present specification. Be incorporated.
- Examples of the ⁇ -hydroxyketone initiator include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, and DAROCUR 1173.
- Omnirad 184 Omnirad 1173
- Omnirad 2959 Omnirad 127
- IRGACURE 184 IRGACURE is a registered trademark
- DAROCUR 1173 DAROCUR 1173
- DAROCUR 1173 DAROCUR 1173.
- -2959, IRGACURE 127 (trade name: both manufactured by BASF) can be used.
- Omnirad 907 As the ⁇ -aminoketone-based initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 369, all of which are IRGACURE 37. (Manufactured by the company) can be used.
- the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used, and the contents thereof are incorporated in the present specification.
- acylphosphine oxide-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- Omnirad 819, Omnirad TPO (all manufactured by IGM Resins BV), IRGACURE-819 and IRGACURE-TPO (trade name: all manufactured by BASF) can be used.
- metallocene compound examples include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem), and the like.
- the photoradical polymerization initiator is more preferably an oxime compound.
- the oxime compound By using the oxime compound, it becomes possible to improve the exposure latitude more effectively.
- the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
- oxime compound examples include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
- an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator.
- IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052).
- a radical polymerization initiator 2) is also preferably used.
- TR-PBG-304, TR-PBG-305 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
- Adeka Arkuru's NCI-730, NCI-831 and Adeka Arkuru's NCI-930 are also used. be able to.
- DFI-091 manufactured by Daito Chemix Co., Ltd.
- SpeedCure PDO manufactured by SARTOMER ARCEMA
- an oxime compound having the following structure can also be used.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081, and the contents thereof are incorporated in the present specification.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such oxime compounds include the compounds described in WO 2013/083505, the contents of which are incorporated herein.
- an oxime compound having a fluorine atom It is also possible to use an oxime compound having a fluorine atom.
- an oxime compound include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013.
- the compound (C-3) and the like described in paragraph 0101 of the publication No. 164471 are mentioned, and the contents thereof are incorporated in the present specification.
- an oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples of the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 are incorporated herein by reference. Further, examples of the oxime compound having a nitro group include ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
- an oxime compound having a benzofuran skeleton can also be used.
- Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
- Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055, and the contents thereof are incorporated in the present specification.
- an oxime compound having an aromatic ring group Ar OX1 having an electron-withdrawing group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
- the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group.
- the benzoyl group may have a substituent.
- the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
- an acyl group or an amino group more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
- the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
- RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
- RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl.
- RX3 to RX14 each independently represent a hydrogen atom or a substituent; However, at least one of RX10 to RX14 is an electron-withdrawing group.
- RX12 is an electron-withdrawing group and RX10 , RX11 , RX13 , and RX14 are hydrogen atoms.
- oxime compound OX examples include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated in the present specification.
- the most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061. Incorporated herein.
- the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl.
- a trihalomethyltriazine compound Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substituted coumarin compound.
- Compounds are preferred.
- photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
- At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is further preferable. ..
- the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
- -Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanol-1, alkylanthraquinone, etc.
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkyl benzoin
- benzyl derivatives such as benzyl dimethyl ketal.
- a compound represented by the following formula (I) can also be used.
- R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
- RI01 is a group represented by the formula (II). It is the same group as RI00 , and RI02 to RI04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.
- R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
- the photoradical polymerization initiator the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used, and the contents thereof are incorporated in the present specification.
- a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
- two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time can be improved.
- Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No.
- the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 0.5% by mass, based on the total solid content of the resin composition of the present invention. It is 15% by mass, more preferably 1.0 to 10% by mass.
- Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range. Since the photopolymerization initiator may also function as a thermal polymerization initiator, cross-linking with the photopolymerization initiator may be further promoted by heating an oven, a hot plate, or the like.
- the resin composition may contain a sensitizer.
- the sensitizer absorbs specific active radiation and becomes an electronically excited state.
- the sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
- the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid or a base.
- Usable sensitizers include benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthracinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazole triazole azo.
- Pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, indigo and the like can be used.
- sensitizer examples include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
- the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. It is more preferably present, and even more preferably 0.5 to 10% by mass.
- the sensitizer may be used alone or in combination of two or more.
- the resin composition of the present invention may contain a chain transfer agent.
- Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
- Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), which is a group of compounds having -S-S-, -SO2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule.
- Dithiobenzoate having a thiocarbonylthio group, trithiocarbonate, dithiocarbamate, xantate compound and the like used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
- thiol compounds can be preferably used.
- the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is further preferable.
- the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a solvent.
- a solvent a known solvent can be arbitrarily used.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
- esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
- alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl propionate, etc.)
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, ethyl 2-alkyl
- ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
- ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
- cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
- sulfoxides for example, dimethyl sulfoxide is preferable.
- N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
- Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
- the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
- the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass.
- the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
- the resin composition of the present invention may contain only one type of solvent, or may contain two or more types of solvent. When two or more kinds of solvents are contained, the total is preferably in the above range.
- the photosensitive resin composition may contain a thermal acid generator.
- the thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
- the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated when the composition is dried after being applied to the substrate (pre-bake: about 70 to 140 ° C.), and when the final heating (cure: about 100 to 400 ° C.) is performed after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
- the thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
- the acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
- aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
- alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
- haloalkyl sulfonic acid such as sulfonic acid is preferable.
- thermoacid generator include those described in paragraph 0055 of JP2013-072935.
- alkyl sulfonic acid having 1 to 4 carbon atoms and haloalkyl sulfonic acid having 1 to 4 carbon atoms are generated. More preferably, methanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonic acid (4-hydroxyphenyl) methylsulfonium, methanesulfonic acid.
- Benzyl acid (4-((methoxycarbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium , Trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonic acid (4-hydroxyphenyl) methylsulfonium, benzyl trifluoromethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) ) Methyl sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3-(5-((
- JP2013-167742A is also preferable as the thermal acid generator.
- the content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin.
- the content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin.
- the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the cured product (cured film) can be further improved.
- 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.
- the resin composition of the present invention may contain a base generator.
- the base generator is a compound capable of generating a base by a physical or chemical action.
- Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
- the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator.
- the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
- the base generator may be an ionic base generator or a nonionic base generator.
- Examples of the base generated from the base generator include secondary amines and tertiary amines.
- the base generator according to the present invention is not particularly limited, and a known base generator can be used.
- Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amineimides.
- Compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, ⁇ -lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
- Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).
- Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
- the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
- Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
- the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
- the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
- a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
- Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably 2 to 24 carbon atoms).
- 2-18 is more preferred, 3-12 is more preferred
- ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
- Rb 1 and Rb 2 may be coupled to each other to form a ring.
- Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
- substituents preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12
- It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
- cyclohexyl groups are more preferred.
- Rb 3 examples include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18). ⁇ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable).
- 7 to 12 are more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24).
- 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbons).
- 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
- a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
- Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
- the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
- Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
- Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited.
- Rb 13 is preferably an arylalkyl group.
- Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
- Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
- 2 to 8 are more preferable, 2 to 3 are more preferable
- aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable
- 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
- Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). , 7-12 is more preferable), and an aryl group is preferable.
- the compound represented by the formula (B1-1) is also preferable.
- Rb 11 and Rb 12 are synonymous with Rb 11 and Rb 12 in the formula (B1-1).
- Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
- Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
- L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting the adjacent oxygen atom and the carbon atom, and the number of atoms on the path of the connecting chain is Represents a hydrocarbon group having 3 or more.
- RN1 and RN2 each independently represent a monovalent organic group.
- linking chain refers to an atomic chain on a path connecting two atoms or a group of atoms to be linked, which is connected at the shortest (minimum number of atoms).
- L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, and the linking chain is composed of four carbon atoms, and is on the path of the linking chain. (That is, the number of atoms constituting the connecting chain, hereinafter also referred to as "linking chain length" or "connecting chain length”) is 4.
- the number of carbon atoms in L in the formula (B3) is preferably 3 to 24.
- the upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
- the lower limit is more preferably 4 or more.
- the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and 5 The following is particularly preferable.
- the chain length of L is preferably 4 or 5, and most preferably 4.
- Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/06614 and the compounds described in paragraph numbers 0143 to 0177 of International Publication No. 2018/038002. Can be mentioned.
- the base generator contains a compound represented by the following formula (N1).
- RN1 and RN2 each independently represent a monovalent organic group
- RC1 represents a hydrogen atom or a protecting group
- L represents a divalent linking group
- L is a divalent linking group, preferably a divalent organic group.
- the linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more.
- the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
- the linking chain length is the number of atoms present in the atomic arrangement that is the shortest route between the two carbonyl groups in the equation.
- RN1 and RN2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 3 to 12 carbon atoms). It is preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), and specifically, an aliphatic hydrocarbon group (preferably 1 to 12 carbon atoms). Is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon can be mentioned. Group is preferred.
- an aliphatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are contained in the aliphatic hydrocarbon chain or the aromatic ring. It may have an oxygen atom in the substituent.
- an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
- a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain.
- Examples thereof include alkyl groups having.
- the linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms.
- the linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group.
- Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
- the cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
- the group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
- Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
- the alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms.
- the alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, alkyl groups having 5 to 12 carbon atoms are preferable for RN1 and RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later.
- a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
- RN1 and RN2 may be connected to each other to form an annular structure.
- oxygen atoms or the like may be contained in the chain.
- the cyclic structure formed by RN1 and RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable.
- a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1) is preferable, and for example, a pyrrol ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, and the like.
- Examples thereof include a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like are preferable.
- RC1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.
- the protecting group a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes by an acid is preferable.
- the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain.
- the chain or cyclic alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and the like.
- Specific examples of the chain-like alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group and the like. Can be mentioned.
- Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group and the like.
- the divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable.
- the hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group.
- a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.
- the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
- the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.
- linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
- a linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
- the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
- the group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
- the alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
- the alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.
- the linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms.
- the cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
- the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
- a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkaneylene group, an arylene group, and an arylene alkylene group are preferable, 1,2-.
- Ethylene group propanediyl group (particularly 1,3-propanediyl group), cyclohexanediyl group (particularly 1,2-cyclohexanediyl group), vinylene group (particularly cisvinylene group), phenylene group (1,2-phenylene group), A phenylene methylene group (particularly 1,2-phenylene methylene group) and an ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
- Examples of the base generator include the following, but the present invention is not construed as being limited thereto.
- the molecular weight of the non-ionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
- the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
- Specific preferable compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
- ammonium salt examples include, but are not limited to, the following compounds.
- iminium salt examples include, but are not limited to, the following compounds.
- the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
- the lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more.
- the upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
- the base generator one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
- the resin composition of the present invention preferably contains a polymerizable compound.
- the polymerizable compound include radical cross-linking agents and other cross-linking agents.
- the resin composition of the present invention preferably contains a radical cross-linking agent.
- the radical cross-linking agent is a compound having a radically polymerizable group.
- a group containing an ethylenically unsaturated bond is preferable.
- Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
- a (meth) acryloyl group As the group containing an ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.
- the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds.
- the radical cross-linking agent may have three or more ethylenically unsaturated bonds.
- As the compound having two or more ethylenically unsaturated bonds a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and 2 to 6 compounds are more preferable.
- the compound having is more preferable.
- the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.
- the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
- the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
- radical cross-linking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate group or an epoxy group, or a monofunctional or polyfunctional group.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group.
- Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
- radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
- examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
- Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acrylic acid, and mixtures thereof.
- the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
- a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
- a preferable radical cross-linking agent other than the above it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
- Compounds having two or more groups and cardo resins can also be used.
- the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.
- dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable.
- SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
- SR-209 manufactured by Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
- DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.
- TPA-330 a trifunctional acrylate having 3 isobutyleneoxy chains
- urethane oligomer UAS-10 are examples of the radical cross-linking agent.
- UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemical Industry Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
- radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765.
- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
- radical cross-linking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.
- the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
- the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
- the radical cross-linking agent provided with the above is more preferable.
- the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
- examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g.
- the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good.
- the acid value is measured according to the description of JIS K 0070: 1992.
- the resin composition it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
- Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 dimethacrylate.
- the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
- a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured product).
- Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
- N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used.
- the monofunctional radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
- the bifunctional or higher functional radical cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
- the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
- One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably within the above range.
- the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
- the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is a reaction of another compound in the composition or a reaction thereof by exposure to the above-mentioned photoacid generator or photobase generator.
- a compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with the product is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof.
- a compound having a plurality of groups in the molecule in which the reaction to be formed is promoted by the action of an acid or a base is preferable.
- the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
- a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group.
- a compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is more preferable.
- an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to an acyloxymethyl group, a methylol group or a methylol group.
- examples thereof include compounds having a structure substituted with an alkoxymethyl group.
- the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
- the cross-linking agent using melamine is a melamine-based cross-linking agent
- the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
- the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
- a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
- the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.
- the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom having the following urea structure, or on triazine.
- the alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
- the total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
- the molecular weight of the above compound is preferably 1500 or less, preferably 180 to 1200.
- R 100 represents an alkyl group or an acyl group.
- R 101 and R 102 each independently represent a monovalent organic group and may be bonded to each other to form a ring.
- Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted with the aromatic group include compounds as shown in the following general formula.
- X represents a single-bonded or divalent organic group
- each R 104 independently represents an alkyl group or an acyl group
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
- R 4 represents a group that decomposes by the action of an acid to produce an alkali-soluble group
- It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R5 represents a group desorbed by the action
- R 105 independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. A + d is 5 or less, b + e is 4 or less, and c + f is 4 or less.
- R 5 in a group that decomposes by the action of an acid to produce an alkali-soluble group a group that is eliminated by the action of an acid, and a group represented by -C (R 4 ) 2 COOR 5 , for example, -C (R 36 ).
- R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may be coupled to each other to form a ring.
- an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
- the alkyl group may be linear or branched.
- cycloalkyl group a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
- the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
- the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
- aralkyl group an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
- the above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
- the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
- R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- These groups are preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group and the like. More preferably, it is a tertiary alkyl ester group or an acetal ester group.
- Examples of the compound having an alkoxymethyl group include the following structures.
- Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group.
- Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
- the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available compound may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
- melamine-based cross-linking agent examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.
- urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol.
- Uril trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl
- Glycoluryl-based cross-linking agents such as; Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea,
- benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
- Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, Dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethyl Examples thereof include benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.
- a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
- Compounds to which the group of the species is directly bonded are also preferably used. Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl.
- suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
- the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
- the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the resin composition of the present invention.
- the epoxy compound preferably contains a polyethylene oxide group.
- the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
- epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propane Triglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, contained silicone.
- n is an integer of 1 to 5
- m is an integer of 1 to 20.
- n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.
- oxetane compound compound having an oxetanyl group
- the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
- examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like.
- Aron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used, and these can be used alone or in combination of two or more. good.
- benzoxazine compound examples include Pd-type benzoxazine, Fa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of a polyhydroxystyrene resin, and a phenol novolac-type dihydrobenzo.
- examples include oxazine compounds. These may be used alone or in combination of two or more.
- the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0. It is more preferably 5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
- the other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfone amide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a ⁇ -ketoester. Examples include compounds and amino compounds.
- silane coupling agent examples include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992.
- examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference.
- silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid.
- Aluminum-based adhesive aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
- the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.3 to 10 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
- the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, it is preferable that the total is in the above range.
- the resin composition of the present invention preferably further contains a migration inhibitor.
- a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the membrane.
- the migration inhibitor is not particularly limited, but has a heterocyclic ring (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
- triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole-based compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
- an ion trap agent that traps anions such as halogen ions can also be used.
- Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656.
- the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used. The content is incorporated herein.
- the migration inhibitor include the following compounds.
- the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass.
- the migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.
- the resin composition of the present invention preferably contains a polymerization inhibitor.
- the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.
- Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxyamine primary cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol
- polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents thereof are described in the present specification. Be incorporated.
- the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
- the polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
- the resin composition of the present invention preferably contains an acid scavenger in order to reduce the change in performance with time from exposure to heating.
- the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having low acidity and high pKa.
- the acid trapping agent a compound having an amino group is preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amine and the like are preferable, and a primary amine, a secondary amine, a tertiary amine and an ammonium salt are preferable.
- the acid scavenger include a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline having a hydroxyl group and / or an ether bond. Derivatives and the like can be preferably mentioned.
- the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator. Is preferable.
- Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzoimidazole and the like.
- As an acid scavenger having a diazabicyclo structure 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4] , 0] Undekar 7-En and the like.
- Examples of the acid trapping agent having an onium structure include tetrabutylammonium hydroxide, triarylsulfoniumhydroxydo, phenacylsulfoniumhydroxydo, sulfoniumhydroxydo having a 2-oxoalkyl group, specifically triphenylsulfoniumhydroxydo and tris (specifically, triphenylsulfonium hydroxide, tris ( Examples thereof include t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
- Examples of the acid scavenger having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
- Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
- Examples of the acid scavenger having a pyridine structure include pyridine, 4-methylpyridine and the like.
- alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like.
- aniline derivative having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline and the like.
- preferred acid trapping agents include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, 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, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N, N-diethylethylenediamine, N, N, N', N'-tetrabutyl-1,6-hexanediamine, spermidin, diaminocyclohexane, bis (2-methoxyethyl) amine, piperidine, methylpiperidin
- the composition according to the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is usually 0.001 to 0 based on the total solid content of the composition. It is 10% by mass, preferably 0.01 to 5% by mass.
- the acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
- the resin composition of the present invention comprises various additives such as a surfactant, a higher fatty acid derivative, a thermal polymerization initiator, an inorganic particle, and an ultraviolet absorber, if necessary, as long as the effects of the present invention can be obtained.
- Organic titanium compounds, antioxidants, antiaggregating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries eg, antifoaming agents, flame retardant agents, etc.
- properties such as film physical characteristics can be adjusted.
- the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
- surfactant various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used.
- the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
- the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. can do. That is, when a film is formed by using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , The applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.
- fluorine-based surfactant examples include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479.
- F482, F554, F780, RS-72-K above, manufactured by DIC Co., Ltd.
- Florard FC430, FC431, FC171, Novek FC4430, FC4432 aboveve, manufactured by 3M Japan Ltd.
- the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used. Incorporated herein.
- a block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated in the present specification.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
- the weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
- a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
- the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.
- silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (all manufactured by Shinetsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
- hydrocarbon-based surfactant examples include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
- organosiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.
- W001 manufactured by Yusho Co., Ltd.
- anion-type surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
- the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.
- the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention.
- the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
- the resin composition of the present invention may contain a thermal polymerization initiator, and may particularly contain a thermal radical polymerization initiator.
- the thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be promoted by adding the thermal radical polymerization initiator, the solvent resistance can be further improved. Further, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
- thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated in the present specification.
- the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
- the resin composition of the present invention may contain inorganic fine particles.
- specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
- the average particle size of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, further preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferable.
- the average particle size of the fine particles is 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, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.
- the composition of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
- salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like
- benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-.
- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned.
- benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3).
- Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.
- the triazine-based ultraviolet absorber 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin
- the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
- the composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
- the resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
- Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
- Specific examples of the organic titanium compound are shown in I) to VII) below:
- I) Titanium chelate compound Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained.
- Specific examples are titanium bis (triethanolamine) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)).
- Titanium Alkoxy Titanium Compounds For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis ⁇ 2,2- (Aryloxymethyl) Butokiside ⁇ ] etc.
- Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
- Monoalkoxytitanium compound For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
- Titanium oxide compound For example, titanium oxide bis (pentangionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
- the organic titanium compound at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing.
- -Pyrrole-1-yl) phenyl) titanium is preferred.
- the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the specific resin.
- the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition Excellent.
- the composition of the present invention may contain an antioxidant.
- an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material.
- the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like.
- the phenol compound any phenol compound known as a phenolic antioxidant can be used.
- Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
- a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
- a phosphorus-based antioxidant can also be preferably used.
- antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like.
- the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification.
- the composition of the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
- Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification.
- Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
- preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
- R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). Represents a group.
- R 7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom.
- k represents an integer of 1 to 4.
- the compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin.
- metal oxidation can be suppressed by the rust preventive action on the metal material.
- k is more preferably an integer of 2 to 4.
- R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
- R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
- Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent.
- alkyl ether group and -NH- from the viewpoint of solubility in a developing solution and metal adhesion
- -NH- is preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. More preferred.
- Examples of the compound represented by the general formula (3) include the following, but the compound is not limited to the following structure.
- the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin.
- the addition amount is 0.1 part by mass or more, the effect of improving the elongation property and the adhesion to the metal material can be easily obtained even in a high temperature and high humidity environment, and when the addition amount is 10 parts by mass or less, for example, the emulsion is exposed.
- the interaction with the agent improves the sensitivity of the resin composition.
- Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present embodiment may contain an anti-aggregation agent, if necessary.
- the antiaggregating agent include sodium polyacrylate and the like.
- one type of anti-aggregation agent may be used alone, or two or more types may be used in combination.
- the composition of the present invention may or may not contain an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.
- the resin composition of the present embodiment may contain a phenolic compound, if necessary.
- phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP.
- one type of phenolic compound may be used alone, or two or more types may be used in combination.
- the composition of the present invention may or may not contain a phenolic compound, but when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.
- Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof.
- the other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.
- one type of other polymer compound may be used alone, or two or more types may be used in combination.
- the composition of the present invention may or may not contain other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
- the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 2,500 mm 2 / s to 8,000 mm. 2 / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film.
- the coating surface condition may deteriorate. ..
- the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is 2.0% or more, the storage stability of the resin composition may be impaired. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
- the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties.
- the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as a complex of an organic compound and a metal are excluded. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
- the resin composition of the present invention selects a raw material having a low metal content as the raw material constituting the resin composition of the present invention.
- examples thereof include a method of filtering the raw materials constituting the product by a filter, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.
- the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
- the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
- ion exchange treatment and the like are preferably mentioned.
- a conventionally known storage container can be used as the storage container for the resin composition of the present invention.
- a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and 6 types of resin are used for the purpose of suppressing contamination of raw materials and the resin composition of the present invention with impurities. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
- the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
- the curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C.
- the form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape.
- the cured product is preferably in the form of a film.
- this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and providing heat dissipation function. You can also choose the shape.
- the film thickness of this cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
- the shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less.
- the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be inferior.
- the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
- the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.
- the resin composition of the present invention can be prepared by mixing each of the above components.
- the mixing method is not particularly limited, and a conventionally known method can be used. For mixing, mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like can be adopted.
- the temperature during mixing is preferably 10 to 30 ° C, more preferably 15 to 25 ° C.
- the filter hole diameter may be, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferable to use HDPE (high density polyethylene).
- the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use.
- filters having different pore diameters or materials may be used in combination.
- the connection mode include a mode in which an HDPE filter having a hole diameter of 1 ⁇ m is connected in series as the first stage and an HDPE filter having a hole diameter of 0.2 ⁇ m is connected in series as the second stage.
- various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration.
- the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.5 MPa or less is more preferable.
- impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
- the adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the resin composition filled in the bottle may be placed under reduced pressure to perform a step of degassing.
- ⁇ Synthesis Example 1 Synthesis of Polymer P-1> 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a 2 liter volume separable flask and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of ⁇ -butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
- ODPA 4,4'-oxydiphthalic acid dianhydride
- HEMA 2-hydroxyethyl methacrylate
- ⁇ -butyrolactone 400 ml of ⁇ -butyrolactone
- the precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
- the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer.
- the produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
- the obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer P-1.
- the weight average molecular weight (Mw) of this polymer P-1 was measured and found to be 20,000.
- the polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain a polymer P-3.
- the weight average molecular weight (Mw) of this polymer P-3 was measured and found to be 18,000.
- Examples and comparative examples> In each example, the components listed in the table below were mixed to obtain each photosensitive resin composition. Further, in the comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of the component shown in the table is the amount described in "Mass part" of the table. Further, in each composition, the solvent content was adjusted so that the solid content concentration of the composition was the value shown in the table. The obtained photosensitive resin composition and comparative composition were pressure-filtered through a polytetrafluoroethylene filter having a filter pore size of 0.8 ⁇ m. Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.
- each photosensitive resin composition or each comparative composition was applied onto a silicon wafer by a spin coating method.
- the silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 20 ⁇ m on the silicon wafer.
- the photosensitive resin composition layer on the silicon wafer is patterned (10 mm ⁇ 50 mm) using a stepper (Nikon NSR 2005 i9C) at an exposure wavelength of 365 nm and an exposure energy of 500 mJ / cm 2 using a photomask. Exposed.
- a developer prepared by mixing the "solvent" and “base” described in the "Developer” column of the table by the mass parts listed in the table is supplied as described in the "Supply method” column of the table.
- the developer was supplied at 100 ml / min for 1 minute using a shower nozzle.
- 100 ml of the developing solution was supplied by a straight nozzle, and paddle development was repeated twice.
- the exposed photosensitive resin composition (resin layer) is heated at a temperature rising rate of 10 ° C./min under a nitrogen atmosphere, and the temperature described in the "Cure temperature (° C.)” column of the table. After reaching the above temperature, the above temperature was maintained for the time described in the “Cure time (min)” column of the table.
- the cured resin layer was immersed in a 4.9 mass% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin layer (cured film). The elongation at break of the resin layer (cured film) obtained above was determined as follows.
- the resin layer (cured film) peeled off above is set to a crosshead speed of 300 mm / min using a tensile tester (Tencilon), and the film is 25 ° C. and 65% relative humidity in the longitudinal (length) direction and width direction.
- the elongation at break was measured in accordance with JIS-K6251: 2017 under the environment of (RH).
- the fracture elongation in each of the longitudinal direction and the width direction was measured 5 times each.
- the arithmetic mean value of the results of a total of 10 measurements of the breaking elongation in the longitudinal direction and the width direction was used as the index value of the breaking elongation.
- the above index value (%) is described in the column of "elongation at break" in the table.
- the numerical value of the elongation at break is high, and 55% or more is accepted.
- the details of the abbreviations described in the columns of "developer” or “rinse” are as follows.
- -NMP N-methyl-2-pyrrolidone-PGMEA: Propylene glycol monomethyl ether acetate-PGME: Propylene glycol monomethyl ether-TMAHaq: 25% by mass aqueous solution of tetramethylammonium hydroxide
- each photosensitive resin composition or comparative composition was applied onto a silicon wafer by a spin coating method.
- the silicon wafer coated with the photosensitive resin composition layer is dried on a hot plate at 100 ° C. for 5 minutes, and the silicon wafer is exposed to a uniform thickness described in the “Film thickness ( ⁇ m)” column of the table.
- a layer of the sex resin composition was formed.
- the photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2 at an exposure wavelength of 365 nm using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer ( The resin layer) was shower-developed and rinsed with each developer for 60 seconds to form holes having a diameter of 10 ⁇ m. Then, in a nitrogen atmosphere, the temperature is raised at a heating rate of 10 ° C./min to reach the temperature described in "Cure temperature (° C.)" in the table, and then described in “Cure time (min)" in the table. Heated for hours.
- the surface of the resin layer is again coated with the same composition as the above-mentioned photosensitive resin composition or the comparative composition, and the photosensitive resin composition is applied in the same manner as above to obtain a patterned film.
- the procedure up to heating for 3 hours was carried out again to form a laminate (1) having two resin layers.
- [Manufacturing of laminated body (2)] The production of the laminate (1) and the production of the laminate (1) by using the same composition as the photosensitive resin composition or the comparative composition used for the production of the laminate (1) on the surface of the laminate (1) obtained above. By repeating the same procedure again, a laminate (2) having four resin layers was produced.
- each photosensitive resin composition or comparative composition was applied onto a silicon wafer by a spin coating method.
- the silicon wafer coated with the photosensitive resin composition layer is dried on a hot plate at 100 ° C. for 5 minutes, and the silicon wafer is exposed to a uniform thickness described in the “Film thickness ( ⁇ m)” column of the table.
- a layer of the sex resin composition was formed.
- the photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was developed.
- the same photosensitive resin composition or comparative composition is used again on the surfaces of the metal layer and the photosensitive resin composition layer, and the photosensitive resin composition is applied to the surface of the patterned film in the same manner as described above.
- the procedure up to heating for 3 hours was carried out again to prepare a laminate (3) composed of a resin layer / metal layer / resin layer.
- a thin copper layer (metal layer) and a resin layer are alternately formed on the surface of the laminate (3) by the same method as that of the laminate (3), and a resin layer / metal layer / resin layer is formed.
- a laminate (4) composed of a / resin layer / metal layer / resin layer was produced.
- the method for producing the cured product according to Comparative Example 1 or Comparative Example 2 uses a developer containing no base. In such an example, it can be seen that the resulting cured film is inferior in elongation at break.
- Example 101 The photosensitive resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a photosensitive resin composition layer having a thickness of 20 ⁇ m, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes.
- NSR1505 i6 a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m
- Example 2 After the above heating, it was developed with the developer used in Example 1 and rinsed with the rinse solution used in Example 1 to obtain a layer pattern. Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 180 ° C., the layer was cured by maintaining for 120 minutes to form an interlayer insulating film for the rewiring layer.
- the interlayer insulating film for the rewiring layer was excellent in insulating property.
- an electronic device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the electronic device operated without any problem.
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Abstract
Description
このような感光性樹脂組成物を、例えば塗布等により基材に適用し、その後、必要に応じて露光、現像、加熱等を行うことにより、ポリイミド前駆体がイミド化された硬化物を基材上に形成することができる。
感光性樹脂組成物は、公知の塗布方法等により適用可能であり、現像により微細なパターン、複雑な形状のパターン等を形成できるため、硬化膜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、ポリイミド前駆体を含む感光性樹脂組成物を用いた硬化物の製造方法について、産業上の応用展開がますます期待されている。 For example, in the above-mentioned applications, a resin such as polyimide is used in the form of a photosensitive resin composition containing a polyimide precursor.
By applying such a photosensitive resin composition to a base material by, for example, coating, and then exposing, developing, heating, etc. as necessary, a cured product in which the polyimide precursor is imidized is used as a base material. Can be formed on top.
The photosensitive resin composition can be applied by a known coating method or the like, and a fine pattern, a pattern having a complicated shape, or the like can be formed by development. It can be said that it is excellent in sex. In addition to the high performance of polyimide, etc., from the viewpoint of excellent manufacturing adaptability, industrial application development of a method for manufacturing a cured product using a photosensitive resin composition containing a polyimide precursor is increasing. It is expected.
特許文献2には、(A)塩基性化合物及び/又は塩基性水溶液、(B)アルコール化合物、(C)N-メチル-2-ピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチレンホスホリックトリアミド、γ-ブチロラクトン、1,3-ジメチル-2-イミダゾリジノン、N-アセチル-ε-カプロラクタム、テトラメチレンスルホンからなる群から選択される少なくとも1種の溶剤並びに(D)ケトン化合物の混合溶剤からなり、(A)を2~15重量部、(B)を25~60重量部、(C)を25~60重量部、(D)を2~15重量部とし、全量が100重量部となるように配合された感光性ポリイミド前駆体用現像液が記載されている。 For example, Patent Document 1 describes at least one selected from the group consisting of (a) basic compounds and (b) amides, ketones, esters, lactones, ethers, halogenated hydrocarbons and hydrocarbons. A developer for a photosensitive polyimide precursor containing one kind of organic solvent is described.
Patent Document 2 describes (A) a basic compound and / or a basic aqueous solution, (B) an alcohol compound, (C) N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, At least one solvent selected from the group consisting of dimethyl sulfoxide, hexamethylenephosphoric triamide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-acetyl-ε-caprolactam, tetramethylene sulfone, as well as (D) is composed of a mixed solvent of a ketone compound, (A) is 2 to 15 parts by weight, (B) is 25 to 60 parts by weight, (C) is 25 to 60 parts by weight, and (D) is 2 to 15 parts by weight. A developer for a photosensitive polyimide precursor, which is blended so that the total amount is 100 parts by weight, is described.
上記硬化物の製造において、低温で硬化した場合であっても破断伸びに優れた硬化物を得ることができる硬化物の製造方法の提供が望まれている。
具体的には、例えば、上記硬化物は再配線層用の層間絶縁膜として使用されている。
ここで、上記絶縁膜が使用される基板は、8インチのウエハサイズから、12インチ、また、パネルレベルのサイズと大面積化が進んでいる。また、銅配線等の配線を設置するために、積層される層数も1層から2層、3層、4層、5層と徐々に増加している。
このような製造時の基盤の大面積化、ポリイミドの層数の増加に伴い、ウエハやパネルの反りが顕著化してきており、上述の加熱を低温(例えば、240℃以下、好ましくは200℃以下、より好ましくは180℃以下)で行うことが望まれている。
しかし、上述の加熱を低温で行った場合には、上記イミド化が十分に進行せず、上記膜の破断伸びが低下してしまう場合があった。 Conventionally, a photosensitive resin composition containing a polyimide precursor is applied to a substrate to form a film, the film is exposed and developed, and then the precursor is imidized by heating to produce a cured product. Has been done. The imidization improves the mechanical properties of the film (eg, elongation at break) and improves the reliability of the module.
In the production of the cured product, it is desired to provide a method for producing the cured product, which can obtain a cured product having excellent elongation at break even when cured at a low temperature.
Specifically, for example, the cured product is used as an interlayer insulating film for the rewiring layer.
Here, the substrate in which the insulating film is used is increasing in area from a wafer size of 8 inches to a size of 12 inches and a panel level. Further, in order to install wiring such as copper wiring, the number of layers to be laminated is gradually increasing from 1 layer to 2 layers, 3 layers, 4 layers and 5 layers.
With the increase in the area of the substrate and the increase in the number of polyimide layers during such manufacturing, the warpage of the wafer and the panel has become remarkable, and the above-mentioned heating is performed at a low temperature (for example, 240 ° C. or lower, preferably 200 ° C. or lower). , More preferably at 180 ° C. or lower).
However, when the above-mentioned heating is performed at a low temperature, the above-mentioned imidization does not proceed sufficiently, and the breaking elongation of the above-mentioned film may decrease.
塩基を感光性樹脂組成物に直接添加する場合、感光性樹脂組成物の保存時においても、ポリイミド前駆体のイミド化が進行してしまい、組成物の粘度が著しく変化してしまう場合があった。
塩基の前駆体である光塩基発生剤を添加した場合、露光時に露光部でネガ画像形成を促進する酸、ラジカルと共に、酸、ラジカルの阻害剤である塩基が同時発生し、感度を低下させる弊害を伴う場合があった。また、処方上、組成物に塩基発生剤を大量に添加することは困難であり、加熱時のイミド化促進の効果は、限定的であった。 So far, attempts have been made to introduce a base into a photosensitive resin composition for the purpose of sufficiently advancing imidization even when heating is performed at a low temperature.
When the base is directly added to the photosensitive resin composition, the imidization of the polyimide precursor may proceed even during storage of the photosensitive resin composition, and the viscosity of the composition may change significantly. ..
When a photobase generator, which is a precursor of a base, is added, an acid and a radical that promote negative image formation in the exposed area are simultaneously generated at the time of exposure, and a base that is an inhibitor of the acid and the radical is generated at the same time, which has an adverse effect of lowering the sensitivity. Was sometimes accompanied. In addition, it is difficult to add a large amount of a base generator to the composition due to the formulation, and the effect of promoting imidization during heating is limited.
<1> 下記式(2)で表される繰り返し単位を有するポリイミド前駆体、及び、光重合開始剤を含む感光性樹脂組成物を基材上に適用して膜を形成する膜形成工程、
上記膜を選択的に露光する露光工程、
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、並びに、
上記現像により得られたパターンを加熱する加熱工程を含み、
上記現像液の全質量に対する水の含有量が50質量%以下である、
硬化物の製造方法。
<2> 上記現像液が、上記塩基として、有機塩基を含む、<1>に記載の硬化物の製造方法。
<3> 上記加熱工程が、加熱により、上記塩基、及び、上記塩基発生剤から発生した塩基よりなる群から選ばれた少なくとも1種の化合物の作用により、上記パターン内で上記ポリイミド前駆体のイミド化を促進する工程である、<1>又は<2>に記載の硬化物の製造方法。
<4> 上記加熱工程における加熱の温度が、120~230℃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> 上記現像工程が、上記現像液を上記露光後の膜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、<1>~<4>のいずれか1つに記載の硬化物の製造方法。
<6> 上記現像工程における現像がネガ型現像である、<1>~<5>のいずれか1つに記載の硬化物の製造方法。
<7> <1>~<6>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、積層体の製造方法。
<8> 上記複数回行われる硬化物の製造方法の間に、硬化物上に金属層を形成する金属層形成工程を更に含む、<7>に記載の積層体の製造方法。
<9> <1>~<6>のいずれか1つに記載の硬化物の製造方法、又は、<7>若しくは<8>に記載の積層体の製造方法を含む、電子デバイスの製造方法。 Examples of typical embodiments of the present invention are shown below.
<1> A film forming step of applying a photosensitive resin composition containing a polyimide precursor having a repeating unit represented by the following formula (2) and a photopolymerization initiator onto a substrate to form a film.
An exposure process that selectively exposes the film,
A developing step of developing a film after exposure to form a pattern with a developing solution containing at least one compound selected from the group consisting of bases and base generators, and
Including a heating step of heating the pattern obtained by the above development.
The content of water with respect to the total mass of the developer is 50% by mass or less.
A method for manufacturing a cured product.
<2> The method for producing a cured product according to <1>, wherein the developer contains an organic base as the base.
<3> In the heating step, the imide of the polyimide precursor is contained in the pattern by the action of at least one compound selected from the group consisting of the base and the base generated from the base generator by heating. The method for producing a cured product according to <1> or <2>, which is a step of promoting the conversion.
<4> The method for producing a cured product according to any one of <1> to <3>, wherein the heating temperature in the heating step is 120 to 230 ° C.
<5> The cured product according to any one of <1> to <4>, wherein the developing step is a step of supplying the developing solution to the exposed film by a shower or continuously supplying the developing solution. Manufacturing method.
<6> The method for producing a cured product according to any one of <1> to <5>, wherein the development in the development step is negative type development.
<7> A method for producing a laminated body, wherein the method for producing a cured product according to any one of <1> to <6> is repeated a plurality of times.
<8> The method for producing a laminate according to <7>, further comprising a metal layer forming step of forming a metal layer on the cured product between the methods for producing the cured product which is performed a plurality of times.
<9> A method for manufacturing an electronic device, which comprises the method for manufacturing a cured product according to any one of <1> to <6>, or the method for manufacturing a laminate according to <7> or <8>.
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。 Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
As used herein, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. Super HZ4000, TSKgel Super HZ3000, and TSKgel
It can be obtained by connecting Super HZ2000 (all manufactured by Tosoh Corporation) in series. Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. However, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as the eluent, such as when the solubility is low. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper". And the opposite direction is called "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Further, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atmospheric pressure), and the relative humidity is 50% RH.
As used herein, a combination of preferred embodiments is a more preferred embodiment.
本発明の硬化物の製造方法は、下記式(2)で表される繰り返し単位を有するポリイミド前駆体(以下、「特定樹脂」ともいう。)、及び、光重合開始剤を含む感光性樹脂組成物を基材上に適用して膜を形成する膜形成工程、上記膜を選択的に露光する露光工程、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、並びに、上記現像により得られたパターンを加熱する加熱工程を含み、上記現像液の全質量に対する水の含有量が50質量%以下である。
The method for producing a cured product of the present invention has a photosensitive resin composition containing a polyimide precursor having a repeating unit represented by the following formula (2) (hereinafter, also referred to as "specific resin") and a photopolymerization initiator. A film forming step of applying an object onto a substrate to form a film, an exposure step of selectively exposing the film, and a developing solution containing at least one compound selected from the group consisting of bases and base generators. The development step of developing the film after the exposure to form a pattern and the heating step of heating the pattern obtained by the development are included, and the content of water with respect to the total mass of the developer is 50% by mass or less. Is.
上記効果が得られるメカニズムは不明であるが、下記のように推測される。 According to the method for producing a cured product of the present invention, a cured product having excellent elongation at break can be obtained even when cured at a low temperature.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
このような現像液を使用することにより、現像時には、現像液に含まれる塩基及び塩基発生剤の少なくとも一方が、現像により得られるパターンに浸透すると考えられる。
上記現像液からパターンへと移行した塩基又は塩基発生剤の少なくとも一方の作用により、上述のポリイミド前駆体は低温であってもイミド化が起こりやすく、加熱時に大幅な低温化を実現することができると推測される。 In the method for producing a cured product of the present invention, a developer containing at least one compound selected from the group consisting of a base and a base generator is used as the developer.
By using such a developer, it is considered that at least one of the base and the base generator contained in the developer permeates the pattern obtained by the development at the time of development.
Due to the action of at least one of the base or the base generator transferred from the developer to the pattern, the polyimide precursor described above is likely to be imidized even at a low temperature, and a significant decrease in temperature can be realized at the time of heating. It is presumed.
以下、本発明の硬化物の製造方法について詳細に説明する。 Here, in Patent Documents 1 and 2, a polyimide precursor having a repeating unit represented by the above formula (2) and a photosensitive resin composition containing a photopolymerization initiator are used, and a base and a base are generated. There is no description of developing the post-exposure film to form a pattern with a developer containing at least one compound selected from the group consisting of agents.
Hereinafter, the method for producing a cured product of the present invention will be described in detail.
本発明の硬化物の製造方法は、感光性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。
本発明において用いられる感光性樹脂組成物(以下、単に「樹脂組成物」ともいう。)の詳細については後述する。 <Membrane formation process>
The method for producing a cured product of the present invention includes a film forming step of applying a photosensitive resin composition onto a substrate to form a film.
Details of the photosensitive resin composition used in the present invention (hereinafter, also simply referred to as “resin composition”) will be described later.
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。 〔Base material〕
The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, Any of a metal base material such as a magnetic film, a reflective film, Ni, Cu, Cr, Fe (for example, a base material formed of metal, or a base material in which a metal layer is formed by, for example, plating or thin film deposition). (May be good), paper, SOG (Spin On Glass), TFT (thin film film) array base material, mold base material, electrode plate of plasma display panel (PDP), and the like, and are not particularly limited. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
Further, the shape of the base material is not particularly limited, and may be circular or rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
Further, as the base material, for example, a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used.
また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
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。 Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity. The method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
Further, a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
Further, a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
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。 <Drying process>
The film may be subjected to a step (drying step) of drying the film (layer) formed to remove the solvent after the film forming step (layer forming step).
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step.
Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.
上記膜は、膜を選択的に露光する露光工程に供される。
すなわち、本発明の硬化物の製造方法は、膜形成工程により形成された膜を選択的に露光する露光工程を含む。
選択的に露光するとは、膜の一部を露光することを意味している。また、選択的に露光することにより、膜には露光された領域(露光部)と露光されていない領域(非露光部)が形成される。
露光量は、本発明の樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で50~10,000mJ/cm2が好ましく、200~8,000mJ/cm2がより好ましい。 <Exposure process>
The film is subjected to an exposure step of selectively exposing the film.
That is, the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed by the film forming step.
Selective exposure means exposing a part of the film. Further, by selectively exposing the film, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
The exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 . Is more preferable.
また、露光の方式は特に限定されず、本発明の樹脂組成物からなる膜の少なくとも一部が露光される方式であればよいが、フォトマスクを使用した露光、レーザーダイレクトイメージング法による露光等が挙げられる。 The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength). 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. Will be. The resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
The exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.
上記膜は、露光後に加熱する工程(露光後加熱工程)に供されてもよい。
すなわち、本発明の硬化物の製造方法は、露光工程により露光された膜を加熱する露光後加熱工程を含んでもよい。
露光後加熱工程は、露光工程後、現像工程前に行うことができる。
露光後加熱工程における加熱温度は、50℃~140℃であることが好ましく、60℃~120℃であることがより好ましい。
露光後加熱工程における加熱時間は、30秒間~300分間が好ましく、1分間~10分間がより好ましい。
露光後加熱工程における昇温速度は、加熱開始時の温度から最高加熱温度まで1~12℃/分が好ましく、2~10℃/分がより好ましく、3~10℃/分が更に好ましい。
また、昇温速度は加熱途中で適宜変更してもよい。
露光後加熱工程における加熱手段としては、特に限定されず、公知のホットプレート、オーブン、赤外線ヒーター等を用いることができる。
また、加熱に際し、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことも好ましい。 <Heating process after exposure>
The film may be subjected to a step of heating after exposure (post-exposure heating step).
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
The post-exposure heating step can be performed after the exposure step and before the developing step.
The heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature.
Further, the heating rate may be appropriately changed during heating.
The heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.
Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.
本発明の硬化物の製造方法は、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含む。
現像を行うことにより、露光部、及び、非露光部の一方が除去され、パターンが形成される。
ここで、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、露光部が現像工程により除去される現像をポジ型現像という。
本発明の硬化物の製造方法に含まれる現像工程における現像は、ネガ型現像であることが好ましい。 <Development process>
The method for producing a cured product of the present invention includes a developing step of developing a film after exposure with a developing solution containing at least one compound selected from the group consisting of a base and a base generator to form a pattern. ..
By performing the development, one of the exposed portion and the non-exposed portion is removed, and a pattern is formed.
Here, the development in which the non-exposed part is removed by the developing process is called negative type development, and the development in which the exposed part is removed by the developing process is called positive type development.
The development in the development step included in the method for producing a cured product of the present invention is preferably negative type development.
本発明の硬化物の製造方法において用いられる現像液は、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種の化合物を含む現像液であって、かつ、現像液の全質量に対する水の含有量が50質量%以下である。
塩基及び塩基発生剤の少なくとも一方を含む現像液を用いた場合には、結果として、加熱後に破断伸びに優れた硬化物が得られている。これは、加熱工程において、パターンに浸漬した現像液中の塩基がイミド化を促進するためであると推測される。
上記水の含有量は、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。 [Developer]
The developer used in the method for producing a cured product of the present invention is a developer containing at least one compound selected from the group consisting of a base and a base generator, and is water with respect to the total mass of the developer. The content is 50% by mass or less.
When a developer containing at least one of a base and a base generator is used, as a result, a cured product having excellent elongation at break after heating is obtained. It is presumed that this is because the base in the developer immersed in the pattern promotes imidization in the heating step.
The content of the water is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 2% by mass or less.
The lower limit of the water content is not particularly limited and may be 0% by mass.
現像液は、少なくとも塩基を含むことが好ましい。
現像液に含まれる塩基としては、硬化後の膜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、又は、アンモニウム塩が好ましく、2級アミン、3級アミン又はアンモニウム塩がより好ましく、2級アミン又は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、硬化膜(得られる硬化物)中に残存しにくいものが好ましく、イミド化促進の観点からは、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。 -base-
The developer preferably contains at least a base.
As the base contained in the developing solution, an organic base is preferable from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated).
Further, as the base, a base having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide and the like are preferable, but in order to promote the imidization reaction, a primary amine is preferable. Secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, and secondary amines or tertiary amines are most preferred.
As the base, a base that does not easily remain in the cured film (obtained cured product) is preferable from the viewpoint of mechanical properties (break elongation) of the cured product, and from the viewpoint of promoting imidization, it is before heating due to vaporization or the like. It is preferable that the residual amount does not easily decrease.
Therefore, the boiling point of the base is preferably 30 ° C. to 350 ° C., more preferably 80 ° C. to 270 ° C., and even more preferably 100 ° C. to 230 ° C. at normal pressure (101,325 Pa).
Further, the boiling point of the base is preferably higher than the temperature obtained by subtracting 20 ° C. from the boiling point of the organic solvent contained in the developing solution, and more preferably higher than the boiling point of the organic solvent contained in the developing solution.
For example, when the boiling point of the organic solvent is 100 ° C., the base used has a boiling point of 80 ° C. or higher, more preferably 100 ° C. or higher.
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0.05~20質量%であることが好ましく、0.1~10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。 When the base is contained, the content of the base with respect to the total mass of the developing solution is preferably 0.01 to 100% by mass, more preferably 0.05 to 20% by mass, and 0.1 to 10% by mass. % Is more preferable.
When the base is not a liquid at 10 to 30 ° C., the content of the base is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass.
The base may be used alone or in combination of two or more. When two or more kinds of bases are used in combination in a developing solution, the total content thereof is preferably within the above range.
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、後述の感光性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。 -Base generator-
The developer may contain a base generator.
Examples of the base generator include a photobase generator or a thermobase generator, and a thermobase generator is preferable.
As the photobase generator or the thermobase generator, for example, the photobase generator or the thermobase generator described as a component contained in the photosensitive resin composition described later can be used without particular limitation.
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。 When the base generator is contained, the content of the base generator with respect to the total mass of the developing solution is preferably 0.1 to 50% by mass, more preferably 0.2 to 20% by mass, and 0. It is more preferably 3 to 10% by mass.
The base generator may be used alone or in combination of two or more. When two or more kinds of base generators are used in combination in a developing solution, the total content thereof is preferably within the above range.
現像液は、現像液の全質量に対して有機溶剤を50質量%以上含むことが好ましく、80質量%以上含むことがより好ましい。上記有機溶剤の含有量の上限は、特に限定されないが、99.9質量%以下であることが好ましく、99.8質量%以下であることがより好ましく、99.5質量%以下であることが更に好ましく、99.0質量%以下であることが特に好ましい。
本発明では、現像液は、ClogP値が-1~5の有機溶剤を含むことが好ましく、ClogP値が0~3の有機溶剤を含むことがより好ましい。ClogP値は、ChemBioDrawにて構造式を入力して計算値として求めることができる。 -solvent-
The developer preferably contains 50% by mass or more of the organic solvent, and more preferably 80% by mass or more, based on the total mass of the developer. The upper limit of the content of the organic solvent is not particularly limited, but is preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and preferably 99.5% by mass or less. It is more preferably 99.0% by mass or less, and particularly preferably 99.0% by mass or less.
In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
また、上述の塩基(例えば、有機塩基)が現像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。 Examples of the organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl propionate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, 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 (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, 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, propylene glycol mono Propyl propionate As acetates and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene. , Anisol, etc., dimethyl sulfoxide as sulfoxides, and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene glycol, etc., and amides. Preferred examples thereof include N-methylpyrrolidone, N-ethylpyrrolidone and dimethylformamide.
Further, when the above-mentioned base (for example, an organic base) is a liquid in an environment where a developing solution is used, the above-mentioned base can be used as a solvent and a base.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The developer may further contain other components.
Examples of other components include known surfactants and known defoaming agents.
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、シャワーノズルが挙げられ、シャワーノズルの1種として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、又はシャワ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、シャワ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。
これらの中でも、現像工程は、現像液を前記露光後の膜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。 [Method of supplying developer]
The method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle. There is a method of paddle development or a method of continuously supplying a developer. The type of nozzle is not particularly limited, and examples thereof include straight nozzles and shower nozzles, and examples of the shower nozzles include spray nozzles and the like.
From the viewpoint of the permeability of the developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a shower nozzle is preferable, and the developing solution to the image area is supplied. From the viewpoint of permeability, the method of supplying with a shower nozzle is more preferable.
Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
The method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
Among these, the developing step is preferably a step of supplying the developing solution to the exposed film by a shower or continuously supplying the developing solution.
リンス液としては、例えば、現像液に含まれる溶剤とは異なる溶剤(例えば、現像液に含まれる有機溶剤とは異なる有機溶剤)を用いることができる。
また、リンス液として、現像液に含まれる溶剤を用いてもよい。
リンス液は、上記溶剤に加えて、水を更に含んでもよい。
また、リンス液は、上述の現像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種の化合物を更に含んでもよい。
リンス時間は、特に限定されないが、例えば5秒~5分間とすることができ、10秒~2分が好ましい。 In the developing step, after the treatment using the developing solution, the pattern may be further washed (rinsed) with the rinsing solution. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
As the rinsing solution, for example, a solvent different from the solvent contained in the developing solution (for example, an organic solvent different from the organic solvent contained in the developing solution) can be used.
Further, the solvent contained in the developing solution may be used as the rinsing solution.
The rinsing liquid may further contain water in addition to the above solvent.
Further, the rinsing solution may further contain at least one compound selected from the group consisting of the base and the base generator contained in the above-mentioned developer.
The rinsing time is not particularly limited, but may be, for example, 5 seconds to 5 minutes, preferably 10 seconds to 2 minutes.
現像工程により得られたパターン(リンス工程を行う場合は、リンス後のパターン)は、上記現像により得られたパターンを加熱する加熱工程に供される。
すなわち、本発明の硬化物の製造方法は、現像工程により得られたパターンを加熱する加熱工程を含む。
また、本発明の硬化物の製造方法は、現像工程を行わずに他の方法で得られたパターン、又は、膜形成工程により得られた膜を加熱する加熱工程を含んでもよい。
加熱工程において、ポリイミド前駆体等の樹脂は環化してポリイミド等の樹脂となる。
また、特定樹脂、又は特定樹脂以外の架橋剤における未反応の架橋性基の架橋なども進行する。
加熱工程における加熱温度(最高加熱温度)としては、50~450℃が好ましく、160~250℃がより好ましく、150~230℃が更に好ましい。 <Heating process>
The pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) is subjected to a heating step of heating the pattern obtained by the above-mentioned development.
That is, the method for producing a cured product of the present invention includes a heating step of heating the pattern obtained by the developing step.
Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step.
In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as polyimide.
In addition, cross-linking of unreacted cross-linking groups with a specific resin or a cross-linking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 160 to 250 ° C, and even more preferably 150 to 230 ° C.
加えて、急速加熱可能なオーブンの場合、加熱開始時の温度から最高加熱温度まで1~8℃/秒の昇温速度で行うことが好ましく、2~7℃/秒がより好ましく、3~6℃/秒が更に好ましい。 The heating in the heating step is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature. The temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, curing is possible. The residual stress of the object can be relaxed.
In addition, in the case of an oven capable of rapid heating, it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. ℃ / sec is more preferable.
上記加熱温度の上限は、350℃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、230℃以下であることが更に好ましく、200℃以下であることが特に好ましい。
その理由は定かではないが、この温度とすることで、層間の特定樹脂のエチニル基同士が架橋反応を進行しているためと考えられる。 In particular, when forming a multi-layered laminate, the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher, from the viewpoint of adhesion between layers of the pattern. It is preferably 120 ° C. or higher, and particularly preferably 120 ° C. or higher.
The upper limit of the heating temperature is preferably 350 ° C. or lower, more preferably 250 ° C. or lower, further preferably 230 ° C. or lower, and particularly preferably 200 ° C. or lower.
The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
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。 Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. It is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
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。 The heating step is preferably carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under reduced pressure in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
本発明の硬化物の製造方法は、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を更に含んでもよい。
現像後露光工程においては、例えば、後述の感光性化合物である光塩基発生剤等が感光し、ポリイミド前駆体の環化が進行して、硬化したパターンが得られる。
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。 <Exposure process after development>
In addition to the heating step, the method for producing a cured product of the present invention may further include a post-development exposure step for exposing the pattern after the developing step.
In the post-development exposure step, for example, a photobase generator or the like, which is a photosensitive compound described later, is exposed to light, cyclization of the polyimide precursor proceeds, and a cured pattern is obtained.
In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity. preferable.
The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.
現像工程により得られたパターン(加熱工程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。 <Metal layer forming process>
The pattern obtained in the developing step (preferably those subjected to the heating step) may be subjected to the metal layer forming step of forming the metal layer on the pattern.
That is, it is preferable that the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one subjected to a heating step).
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。 <Use>
Examples of the method for producing a cured product of the present invention or the applicable field of the cured product of the present invention include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.
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。 (Laminated body and method for manufacturing the laminated body)
The laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
The laminated body of the present invention is a laminated body including two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
Of the two or more layers made of the cured product contained in the laminated body, at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.
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。 It is preferable that the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times. The preferred embodiment of the metal layer forming step is as described above.
As the above-mentioned laminate, for example, a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done.
It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
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)加熱工程を繰り返す態様であってもよい。また、(d)加熱工程の後には(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。 <Laminating process>
The method for producing a laminated body of the present invention preferably includes a laminating step.
The laminating step is a process of (a) film forming step (layer forming step), (b) exposure step, (c) developing step, and (d) heating step again on the surface of the pattern (resin layer) or metal layer. It is a series of steps including performing in this order. However, it may be an embodiment in which the film forming step (a) and the heating step (d) are repeated. Further, (d) the heating step may be followed by (e) a metal layer forming step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.
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。 The laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, a structure having two or more and 20 or less resin layers, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
The composition, shape, film thickness, etc. of each of the above layers may be the same or different.
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、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。 (Surface activation treatment process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer forming step, but after the development step, the surface activation treatment step may be performed on the resin composition layer, and then the metal layer forming step may be performed.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the exposed resin composition layer, or on the metal layer and the exposed resin composition layer. For both, you may go to at least part of each. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region forming the resin composition layer on the surface of the metal layer. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment. In particular, when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2 . , 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 oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. In the case of the corona discharge treatment, the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , and most preferably 10,000 to 50,000 J / m 2 .
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電子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電子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。 (Manufacturing method of electronic device)
The present invention also discloses a method for producing a cured product of the present invention, or a method for producing an electronic device including a method for producing a laminate of the present invention. As specific examples of the electronic device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
感光性樹脂組成物は、本発明の硬化物の製造方法、本発明の積層体の製造方法、又は、本発明の電子デバイスの製造方法において用いられる感光性樹脂組成物である。
本発明の感光性樹脂組成物は、式(2)で表される繰り返し単位を有するポリイミド前駆体、及び、光重合開始剤を含む。
以下、本発明の感光性樹脂組成物に含まれる、各成分の詳細について説明する。 (Photosensitive resin composition)
The photosensitive resin composition is a photosensitive resin composition used in the method for producing a cured product of the present invention, the method for producing a laminate of the present invention, or the method for producing an electronic device of the present invention.
The photosensitive resin composition of the present invention contains a polyimide precursor having a repeating unit represented by the formula (2) and a photopolymerization initiator.
Hereinafter, the details of each component contained in the photosensitive resin composition of the present invention will be described.
感光性樹脂組成物は、式(2)で表される繰り返し単位を有するポリイミド前駆体(特定樹脂)を含む。
また、特定樹脂はラジカル重合性基を有することが好ましい。
特定樹脂がラジカル重合性基を有する場合、感光性樹脂組成物は、光重合開始剤として後述の光ラジカル重合開始剤を含むことが好ましく、後述の光ラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましく、後述の光ラジカル重合開始剤を含み、後述のラジカル架橋剤を含み、かつ、後述の増感剤を含むことが更に好ましい。このような感光性樹脂組成物からは、例えば、ネガ型感光層が形成される。
また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
特定樹脂が酸分解性基を有する場合、感光性樹脂組成物は、後述の光酸発生剤を含むことが好ましい。このような感光性樹脂組成物からは、例えば、化学増幅型であるポジ型感光層又はネガ型感光層が形成される。 <Specific resin>
The photosensitive resin composition contains a polyimide precursor (specific resin) having a repeating unit represented by the formula (2).
Further, the specific resin preferably has a radically polymerizable group.
When the specific resin has a radically polymerizable group, the photosensitive resin composition preferably contains a photoradical polymerization initiator described later as a photopolymerization initiator, and also contains a photoradical polymerization initiator described below and is described later. It is more preferable to contain a radical cross-linking agent, and further preferably to contain a photoradical polymerization initiator described later, a radical cross-linking agent described later, and a sensitizer described later. From such a photosensitive resin composition, for example, a negative photosensitive layer is formed.
Further, the specific resin may have a polar conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably contains a photoacid generator described later. From such a photosensitive resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.
本発明で用いるポリイミド前駆体は、下記式(2)で表される繰り返し単位を含む。
The polyimide precursor used in the present invention contains a repeating unit represented by the following formula (2).
式(2)におけるR111は、2価の有機基を表す。2価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数3~20の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基を含む基がより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく、上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。本発明の好ましい実施形態として、-Ar-および-Ar-L-Ar-で表される基であることが例示され、特に好ましくは-Ar-L-Ar-で表される基である。但し、Arは、それぞれ独立に、芳香族基であり、Lは、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-又は-NHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 A 1 and A 2 in the formula (2) independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.
R 111 in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified. A cyclic aliphatic group having 3 to 20, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a group containing. Preferred embodiments of the present invention are exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be single-bonded or substituted with a fluorine atom, -O-, -CO. -, -S-, -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.
具体的には、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数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。 R 111 is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a containing group. Examples of groups containing aromatic groups include:
式中、*は他の構造との結合部位を表す。
In the formula, * represents a binding site with another structure.
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。 Further, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)
The monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
Examples of the diamine giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and 2,2'-bis. (Fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
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。
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
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。 R 113 and R 114 in the formula (2) each independently represent a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Further, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that 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. As the polymerizable group, a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group and an amino group. Be done. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to the vinyl group (for example, a vinylphenyl group), and a (meth) acrylamide group. , (Meta) acryloyloxy group, a group represented by the following formula (III) and the like, and a group represented by the following formula (III) is preferable.
式(III)において、*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。 In formula (III), R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.
In formula (III), * represents a binding site with another structure.
In formula (III), 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.
Examples of suitable R 201 include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, alkylene group such as ethylene group, propylene group, -CH 2 CH (OH) CH 2- , cyclohexyl group, polyalkylene An oxy group is more preferable, and an alkylene group such as an ethylene group and a propylene group, or a polyalkylene oxy group is further preferable.
In the present invention, the polyalkyleneoxy group refers to a group to which two or more alkyleneoxy groups are directly bonded. The alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
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。 In formula (2), at least one of R 113 and R 114 may be a polar conversion group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl. Examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
式(2-A)
Equation (2-A)
R112は、式(5)におけるR112と同義であり、好ましい範囲も同様である。 A 1 , A 2 , R 111 , R 113 , and R 114 are independently synonymous with A 1 , A 2 , R 111 , R 113 , and R 114 in the formula (2), and the preferred ranges are also the same. ..
R 112 has the same meaning as R 112 in the formula (5), and the preferred range is also the same.
上記ポリイミド前駆体の分子量の分散度は、1.8以上が好ましく、2.0以上がより好ましく、2.2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。 The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 8,000 to 20,000.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.8 or more, more preferably 2.0 or more, and further preferably 2.2 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
When the resin composition contains a plurality of types of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion of at least one type of polyimide precursor are in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyimide precursors as one resin are within the above ranges.
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。 [Manufacturing method of polyimide precursor, etc.]
The polyimide precursor and the like can be, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature, or reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature to obtain a polyamic acid, and a condensing agent or an alkylating agent. A method of esterifying with tetracarboxylic acid dianhydride and alcohol to obtain a diester, and then reacting with diamine in the presence of a condensing agent, a method of obtaining a diester with tetracarboxylic acid dianhydride and alcohol. After that, the remaining dicarboxylic acid can be obtained by acid-halogenizing it with a halogenating agent and reacting it with a diamine. Among the above-mentioned production methods, a method in which a diester is obtained from tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated with a halogenating agent and reacted with a diamine is more preferable.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples thereof include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
Examples of the alkylating agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethylacetal, N, N-dialkylformamidedialkylacetal, trimethyl orthoformate, triethyl orthoformate and the like.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, but is pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone and the like. Is exemplified.
In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.
The basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, N, N-dimethyl-4-amino. Examples thereof include pyridine and the like.
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必要である。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。また、特に、反応性、膜の安定性から、アルコール類、フェノール類が好ましく、アルコール類がより好ましい。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。 -End sealant-
In the method of producing a polyimide precursor or the like, in order to further improve the storage stability, it is necessary to seal the carboxylic acid anhydride, the acid anhydride derivative, or the amino group remaining at the resin terminal of the polyimide precursor or the like. be. When encapsulating the carboxylic acid anhydride and the acid anhydride derivative remaining at the resin terminal, examples of the terminal encapsulant include monoalcohol, phenol, thiol, thiophenol, monoamine, etc., and are reactive and stable in the film. From the viewpoint of properties, it is more preferable to use monoalcohol, phenols and monoamines. Further, in particular, alcohols and phenols are preferable, and alcohols are more preferable, from the viewpoint of reactivity and membrane stability. Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and flufuryl alcohol, and isopropanol. , 2-Butanol, cyclohexyl alcohol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, t-butyl alcohol, adamantan alcohol and other tertiary alcohols. Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and hydroxystyrene. Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-. Aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -Aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Can be mentioned. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.
Further, when sealing the amino group at the end of the resin, it is possible to seal with a compound having a functional group capable of reacting with the amino group. Preferred encapsulants for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, anhydrous sulfonic acids, sulfonic acid carboxylic acid anhydrides and the like, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable. Preferred compounds for carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornen-2,3-dicarboxylic acid anhydride and the like. Can be mentioned. Preferred compounds for the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride and 1-adamantancarbonyl chloride. , Heptafluorobutyryl chloride, stearate chloride, benzoyl chloride, and the like.
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。 -Solid precipitation-
A step of precipitating a solid may be included in the production of a polyimide precursor or the like. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution was filtered off as necessary, and then obtained in a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof. By adding the polymer component and precipitating the polymer component, it is precipitated as a solid, and by drying, a polyimide precursor or the like can be obtained. In order to improve the degree of purification, operations such as redissolution, reprecipitation and drying of the polyimide precursor may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.
本発明の樹脂組成物における特定樹脂の含有量は、樹脂組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明の樹脂組成物における樹脂の含有量は、樹脂組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
本発明の樹脂組成物は、特定樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 〔Content〕
The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the resin composition. More preferably, it is more preferably 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the resin composition. % Or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
具体的には、本発明の樹脂組成物は、特定樹脂と、後述する他の樹脂とを合計で2種以上含んでもよいし、特定樹脂を2種以上含んでいてもよいが、特定樹脂を2種以上含むことが好ましい。
本発明の樹脂組成物が特定樹脂を2種以上含む場合、例えば、ポリイミド前駆体であって、二無水物由来の構造(上述の式(2)でいうR115)が異なる2種以上のポリイミド前駆体を含むことが好ましい。 Further, it is also preferable that the resin composition of the present invention contains at least two kinds of resins.
Specifically, the resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but the specific resin may be contained. It is preferable to include two or more kinds.
When the resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimides which are polyimide precursors and have different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to include a precursor.
本発明の樹脂組成物は、上述した特定樹脂と、特定樹脂とは異なる他の樹脂(以下、単に「他の樹脂」ともいう)とを含んでもよい。
他の樹脂としては、ポリアミドイミド、ポリアミドイミド前駆体、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、(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50,000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。 <Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
Other resins include polyamide-imide, polyamide-imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth) acrylic resins, (meth) acrylamide resins, urethane resins, butyral resins, styryl. Examples thereof include resins, polyether resins, and polyester resins.
For example, by further adding a (meth) acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a high polymerizable base value having a weight average molecular weight of 50,000 or less (for example, the molar amount of the polymerizable group contained in 1 g of the resin). (1 × 10 -3 mol / g or more) By adding a (meth) acrylic resin to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
また、本発明の樹脂組成物における、他の樹脂の含有量は、樹脂組成物の全固形分に対し、30質量%以下であることが好ましく、20質量%以下であることがより好ましく、10質量%以下であることが更に好ましい。
本発明の樹脂組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present invention contains another resin, the content of the other resin may be more than 0% by mass, but is 0.1% by mass or more, based on the total solid content of the resin composition. It is preferably 0.5% by mass or more, and more preferably 0.5% by mass or more.
Further, the content of other resins in the resin composition of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the resin composition. It is more preferably mass% or less.
The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
感光性樹脂組成物は、光重合開始剤を含む。
光重合開始剤は、光ラジカル重合開始剤であることが好ましい。光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。 [Photopolymerization initiator]
The photosensitive resin composition contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
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。 The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl. Represents a sulfonyl group, an acyloxy group or an amino group
RX3 to RX14 each independently represent a hydrogen atom or a substituent;
However, at least one of RX10 to RX14 is an electron-withdrawing group.
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。 The content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 0.5% by mass, based on the total solid content of the resin composition of the present invention. It is 15% by mass, more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.
Since the photopolymerization initiator may also function as a thermal polymerization initiator, cross-linking with the photopolymerization initiator may be further promoted by heating an oven, a hot plate, or the like.
樹脂組成物は、増感剤を含んでいてもよい。増感剤は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸又は塩基を生成する。
使用可能な増感剤として、ベンゾフェノン系、ミヒラーズケトン系、クマリン系、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アントラセン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ペンゾピラン系、インジゴ系等の化合物を使用することができる。
増感剤としては、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン(7-(ジエチルアミノ)クマリン-3-カルボン酸エチル)、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンゾチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン、ジフェニルアセトアミド、ベンズアニリド、N-メチルアセトアニリド、3‘,4’-ジメチルアセトアニリド等が挙げられる。
また、他の増感色素を用いてもよい。
増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。 [Sensitizer]
The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid or a base.
Usable sensitizers include benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthracinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazole triazole azo. , Pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, indigo and the like can be used.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 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-dimethylaminophenylbinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) iso Naftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3 -Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Kumarin (7- (diethylamino) coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, Isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethyl) Aminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4 '-Dimethylacetanilide and the like can be mentioned.
Moreover, you may use other sensitizing dyes.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027355 can be referred to, and the content thereof is incorporated in the present specification.
本発明の樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内に-S-S-、-SO2-S-、-N-O-、SH、PH、SiH、及びGeHを有する化合物群、RAFT(Reversible Addition Fragmentation chain Transfer)重合に用いられるチオカルボニルチオ基を有するジチオベンゾアート、トリチオカルボナート、ジチオカルバマート、キサンタート化合物等が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、若しくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物を好ましく用いることができる。 [Chain transfer agent]
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), which is a group of compounds having -S-S-, -SO2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule. ) Dithiobenzoate having a thiocarbonylthio group, trithiocarbonate, dithiocarbamate, xantate compound and the like used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.
本発明の樹脂組成物は、溶剤を含むことが好ましい。
溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、環状炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。 <Solvent>
The resin composition of the present invention preferably contains a solvent.
As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
感光性樹脂組成物は、熱酸発生剤を含んでもよい。
熱酸発生剤は、加熱により酸を発生し、ヒドロキシメチル基、アルコキシメチル基又はアシルオキシメチル基を有する化合物、エポキシ化合物、オキセタン化合物及びベンゾオキサジン化合物から選ばれる少なくとも1種の化合物の架橋反応を促進させる効果がある。 <Thermal acid generator>
The photosensitive resin composition may contain a thermal acid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
熱分解開始温度は、熱酸発生剤を耐圧カプセル中5℃/分で500℃まで加熱した場合に、最も温度が低い発熱ピークのピーク温度として求められる。
熱分解開始温度を測定する際に用いられる機器としては、Q2000(TAインスツルメント社製)等が挙げられる。 The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated when the composition is dried after being applied to the substrate (pre-bake: about 70 to 140 ° C.), and when the final heating (cure: about 100 to 400 ° C.) is performed after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
本発明の樹脂組成物は、塩基発生剤を含んでもよい。ここで、塩基発生剤とは、物理的または化学的な作用によって塩基を発生することができる化合物である。本発明の樹脂組成物にとって好ましい塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。
特に、樹脂組成物が環化樹脂の前駆体を含む場合、樹脂組成物は塩基発生剤を含むことが好ましい。樹脂組成物が熱塩基発生剤を含有することによって、例えば加熱により前駆体の環化反応を促進でき、硬化物の機械特性や耐薬品性が良好なものとなり、例えば半導体パッケージ中に含まれる再配線層用層間絶縁膜としての性能が良好となる。
塩基発生剤としては、イオン型塩基発生剤でもよく、非イオン型塩基発生剤でもよい。塩基発生剤から発生する塩基としては、例えば、2級アミン、3級アミンが挙げられる。
本発明に係る塩基発生剤について特に制限はなく、公知の塩基発生剤を用いることができる。公知の塩基発生剤としては、例えば、カルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール誘導体化合物、アミンイミド化合物、ピリジン誘導体化合物、α-アミノアセトフェノン誘導体化合物、4級アンモニウム塩誘導体化合物、ピリジニウム塩、α-ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド誘導体化合物、アシルオキシイミノ化合物、などを用いることができる。
非イオン型塩基発生剤の具体的な化合物としては、式(B1)、式(B2)、又は式(B3)で表される化合物が挙げられる。
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by a physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator according to the present invention is not particularly limited, and a known base generator can be used. Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amineimides. Compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).
Rb13はアルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Rb13はアリールアルキル基が好ましい。 In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited. Among them, Rb 13 is preferably an arylalkyl group.
Rb15及びRb16は水素原子、アルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~11が更に好ましい)であり、水素原子又はメチル基が好ましい。
Rb17はアルキル基(炭素数1~24が好ましく、1~12がより好ましく、3~8が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~10がより好ましく、3~8が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、中でもアリール基が好ましい。 Rb 11 and Rb 12 are synonymous with Rb 11 and Rb 12 in the formula (B1-1).
Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
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。 As the aliphatic hydrocarbon group constituting RN1 and RN2 , a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain. Examples thereof include alkyl groups having. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. The linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group. Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
The group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
The alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
Among them, alkyl groups having 5 to 12 carbon atoms are preferable for RN1 and RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later. However, in a formulation that emphasizes adhesion when laminated with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
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。 The divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group. A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.
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。 Specific examples of the linking group L include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain. , A linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
The group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.
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。 The linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. The linear or branched chain-like alkenylene group preferably has 1 to 10 C = C bonds, more preferably 1 to 6, and even more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. For the cyclic alkenylene group, the number of C = C bonds is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 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.
Of these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkaneylene group, an arylene group, and an arylene alkylene group are preferable, 1,2-.
Ethylene group, propanediyl group (particularly 1,3-propanediyl group), cyclohexanediyl group (particularly 1,2-cyclohexanediyl group), vinylene group (particularly cisvinylene group), phenylene group (1,2-phenylene group), A phenylene methylene group (particularly 1,2-phenylene methylene group) and an ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
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。 When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
As the base generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
本発明の樹脂組成物は、重合性化合物を含むことが好ましい。
重合性化合物としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。 <Polymerizable compound>
The resin composition of the present invention preferably contains a polymerizable compound.
Examples of the polymerizable compound include radical cross-linking agents and other cross-linking agents.
本発明の樹脂組成物は、ラジカル架橋剤を含むことが好ましい。
ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基、マレイミド基、(メタ)アクリルアミド基などのエチレン性不飽和結合を有する基が挙げられる。
これらの中でも、上記エチレン性不飽和結合を含む基としては、(メタ)アクリロイル基、(メタ)アクリルアミド基、ビニルフェニル基が好ましく、反応性の観点からは、(メタ)アクリロイル基がより好ましい。 [Radical cross-linking agent]
The resin composition of the present invention preferably contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
Among these, as the group containing an ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.
上記エチレン性不飽和結合を2個以上有する化合物としては、エチレン性不飽和結合を2~15個有する化合物が好ましく、エチレン性不飽和結合を2~10個有する化合物がより好ましく、2~6個有する化合物が更に好ましい。
また、得られるパターン(硬化物)の膜強度の観点からは、本発明の樹脂組成物は、エチレン性不飽和結合を2個有する化合物と、上記エチレン性不飽和結合を3個以上有する化合物とを含むことも好ましい。 The radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds. The radical cross-linking agent may have three or more ethylenically unsaturated bonds.
As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and 2 to 6 compounds are more preferable. The compound having is more preferable.
Further, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.
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EO付加物ジメタリレート、2-ヒドロキシー3-アクリロイロキシプロピルメタクリレート、イソシアヌル酸EO変性ジアクリレート、イソシアヌル酸変性ジメタクリレート、その他ウレタン結合を有する2官能アクリレート、ウレタン結合を有する2官能メタクリレートを使用することができる。これらは必要に応じ、2種以上を混合し使用することができる。
なお、例えばPEG200ジアクリレートとは、ポリエチレングリコールジアクリレートであって、ポリエチレングリコール鎖の式量が200程度のものをいう。
本発明の樹脂組成物は、パターン(硬化物)の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、グリシジル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸誘導体、N-ビニルピロリドン、N-ビニルカプロラクタム等のN-ビニル化合物類、アリルグリシジルエーテル等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で100℃以上の沸点を持つ化合物も好ましい。
その他、2官能以上のラジカル架橋剤としては、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類が挙げられる。 As the resin composition, it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 dimethacrylate. Methacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate, 3-Methyl-1,5-Pentanediol Diacrylate, 1,6-Hexanediol Diacrylate, 1,6 hexanediol dimethacrylate, dimethyrole-tricyclodecanediacrylate, dimethyrole-tricyclodecanedimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethalilate of bisphenol A, PO (propylene of bisphenol A) Oxide) Additive Diacrylate, EO Additive Dimethacrylate of Bisphenol A, 2-Hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylate with urethane bond, urethane bond Bifunctional methacrylate having the above can be used. If necessary, two or more of these can be mixed and used.
For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
In the resin composition of the present invention, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured product). Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
Other examples of the bifunctional or higher functional radical cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
本発明の樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことも好ましい。
本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の光酸発生剤、又は、光塩基発生剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
上記酸又は塩基は、露光工程において、光酸発生剤又は光塩基発生剤から発生する酸又は塩基であることが好ましい。
他の架橋剤としては、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基を有する化合物が好ましく、アシルオキシメチル基、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をアシルオキシメチル基、メチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
これらの中でも、本発明の樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことがより好ましい。 [Other cross-linking agents]
It is also preferable that the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is a reaction of another compound in the composition or a reaction thereof by exposure to the above-mentioned photoacid generator or photobase generator. A compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with the product is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof. A compound having a plurality of groups in the molecule in which the reaction to be formed is promoted by the action of an acid or a base is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group. A compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to an acyloxymethyl group, a methylol group or a methylol group. Examples thereof include compounds having a structure substituted with an alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.
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。 As the compound containing at least one of the alkoxymethyl group and the acyloxymethyl group in the present invention, the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom having the following urea structure, or on triazine. Can be mentioned as a structural example.
The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the above compound is preferably 1500 or less, preferably 180 to 1200.
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。 R 100 represents an alkyl group or an acyl group.
R 101 and R 102 each independently represent a monovalent organic group and may be bonded to each other to form a ring.
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。 In the formula, X represents a single-bonded or divalent organic group, each R 104 independently represents an alkyl group or an acyl group, and R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group. , Or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is desorbed by the action of an acid, a group represented by -C (R 4 ) 2 COOR 5 (R 4 is independent of each other). It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a group desorbed by the action of an acid.)).
R 105 independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. A + d is 5 or less, b + e is 4 or less, and c + f is 4 or less.
For R 5 in a group that decomposes by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and a group represented by -C (R 4 ) 2 COOR 5 , for example, -C (R 36 ). ) (R 37 ) (R 38 ), -C (R 36 ) (R 37 ) (OR 39 ), -C (R 01 ) (R 02 ) (OR 39 ) and the like.
In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be coupled to each other to form a ring.
As the 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.
As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
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。 As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound may be used, or a compound synthesized by a known method may be used.
From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノジエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
1,3-ジ(メトキシメチル)4,5-ジヒドロキシ-2-イミダゾリジノン、1,3-ジ(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリジノンなどが挙げられる。 Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol. Uril, trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl Glycoluryl-based cross-linking agents such as;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.
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。 Specific examples of the benzoguanamine-based cross-linking agent 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 Examples thereof include benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.
このような化合物の具体例としては、ベンゼンジメタノール、ビス(ヒドロキシメチル)クレゾール、ビス(ヒドロキシメチル)ジメトキシベンゼン、ビス(ヒドロキシメチル)ジフェニルエーテル、ビス(ヒドロキシメチル)ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス(ヒドロキシメチル)ビフェニル、ジメチルビス(ヒドロキシメチル)ビフェニル、ビス(メトキシメチル)ベンゼン、ビス(メトキシメチル)クレゾール、ビス(メトキシメチル)ジメトキシベンゼン、ビス(メトキシメチル)ジフェニルエーテル、ビス(メトキシメチル)ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス(メトキシメチル)ビフェニル、ジメチルビス(メトキシメチル)ビフェニル、4,4’,4’’-エチリデントリス[2,6-ビス(メトキシメチル)フェノール]、5,5’-[2,2,2‐トリフルオロ‐1‐(トリフルオロメチル)エチリデン]ビス[2‐ヒドロキシ‐1,3‐ベンゼンジメタノール]、3,3’,5,5’-テトラキス(メトキシメチル)-1,1’-ビフェニル-4,4’-ジオール等が挙げられる。 In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which the group of the species is directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Examples thereof include methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like.
エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、本発明の樹脂組成物の低温硬化及び反りの抑制に効果的である。 -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 lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low temperature curing and warpage of the resin composition of the present invention.
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。 -Oxetane compound (compound having an oxetanyl group)-
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, Aron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used, and these can be used alone or in combination of two or more. good.
ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。 -Benzoxazine compound (compound having a benzoxazolyl group)-
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
本発明の樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、アルコキシシリル基を有するシランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物などが挙げられる。 <Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfone amide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a β-ketoester. Examples include compounds and amino compounds.
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。 〔Silane coupling agent〕
Examples of the silane coupling agent include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992. The compounds described in 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group.
アルミニウム系接着助剤としては、例えば、アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。 [Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
本発明の樹脂組成物は、マイグレーション抑制剤を更に含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層(金属配線)由来の金属イオンが膜内へ移動することを効果的に抑制可能となる。 <Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the membrane.
本発明の樹脂組成物は、重合禁止剤を含むことが好ましい。重合禁止剤としてはフェノール系化合物、キノン系化合物、アミノ系化合物、N-オキシルフリーラジカル化合物系化合物、ニトロ系化合物、ニトロソ系化合物、ヘテロ芳香環系化合物、金属化合物などが挙げられる。 <Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.
本発明の樹脂組成物は、露光から加熱までの経時による性能変化を低減するために、酸捕捉剤を含有することが好ましい。ここで酸捕捉剤とは、系中に存在することで発生酸を捕捉することができる化合物を指し、酸性度が低くpKaの高い化合物であることが好ましい。酸捕捉剤としては、アミノ基を有する化合物が好ましく、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く、1級アミン、2級アミン、3級アミン、アンモニウム塩が好ましく、2級アミン、3級アミン、アンモニウム塩がより好ましい。
酸捕捉剤としては、イミダゾール構造、ジアザビシクロ構造、オニウム構造、トリアルキルアミン構造、アニリン構造又はピリジン構造を有する化合物、水酸基及び/又はエーテル結合を有するアルキルアミン誘導体、水酸基及び/又はエーテル結合を有するアニリン誘導体等を好ましく挙げることができる。オニウム構造を有する場合、酸捕捉剤はアンモニウム、ジアゾニウム、ヨードニウム、スルホニウム、ホスホニウム、ピリジニウムなどから選択されるカチオンと、酸発生剤が発生する酸より酸性度の低い酸のアニオンとを有する塩であることが好ましい。 <Acid scavenger>
The resin composition of the present invention preferably contains an acid scavenger in order to reduce the change in performance with time from exposure to heating. Here, the acid scavenger refers to a compound that can capture the generated acid by being present in the system, and is preferably a compound having low acidity and high pKa. As the acid trapping agent, a compound having an amino group is preferable, a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amine and the like are preferable, and a primary amine, a secondary amine, a tertiary amine and an ammonium salt are preferable. Is preferable, and secondary amines, tertiary amines, and ammonium salts are more preferable.
Examples of the acid scavenger include a compound having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline having a hydroxyl group and / or an ether bond. Derivatives and the like can be preferably mentioned. When having an onium structure, the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator. Is preferable.
ジアザビシクロ構造を有する酸捕捉剤としては1、4-ジアザビシクロ[2,2,2]オクタン、1、5-ジアザビシクロ[4,3,0]ノナ-5-エン、1、8-ジアザビシクロ[5,4,0]ウンデカー7-エン等が挙げられる。オニウム構造を有する酸捕捉剤としてはテトラブチルアンモニウムヒドロキシド、トリアリールスルホニウムヒドロキシド、フェナシルスルホニウムヒドロキシド、2-オキソアルキル基を有するスルホニウムヒドロキシド、具体的にはトリフェニルスルホニウムヒドロキシド、トリス(t-ブチルフェニル)スルホニウムヒドロキシド、ビス(t-ブチルフェニル)ヨードニウムヒドロキシド、フェナシルチオフェニウムヒドロキシド、2-オキソプロピルチオフェニウムヒドロキシド等が挙げられる。トリアルキルアミン構造を有する酸捕捉剤としては、トリ(n-ブチル)アミン、トリ(n-オクチル)アミン等を挙げることができる。アニリン構造を有する酸捕捉剤としては、2,6-ジイソプロピルアニリン、N,N-ジメチルアニリン、N,N-ジブチルアニリン、N,N-ジヘキシルアニリン等を挙げることができる。
ピリジン構造を有する酸捕捉剤としては、ピリジン、4-メチルピリジン等を挙げることができる。水酸基及び/又はエーテル結合を有するアルキルアミン誘導体としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、N-フェニルジエタノールアミン、トリス(メトキシエトキシエチル)アミン等を挙げることができる。水酸基及び/又はエーテル結合を有するアニリン誘導体としては、N,N-ビス(ヒドロキシエチル)アニリン等を挙げることができる。 Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzoimidazole and the like.
As an acid scavenger having a diazabicyclo structure, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4] , 0] Undekar 7-En and the like. Examples of the acid trapping agent having an onium structure include tetrabutylammonium hydroxide, triarylsulfoniumhydroxydo, phenacylsulfoniumhydroxydo, sulfoniumhydroxydo having a 2-oxoalkyl group, specifically triphenylsulfoniumhydroxydo and tris (specifically, triphenylsulfonium hydroxide, tris ( Examples thereof include t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of the acid scavenger having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
Examples of the acid scavenger having a pyridine structure include pyridine, 4-methylpyridine and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.
本発明に係る組成物は、酸捕捉剤を含有してもしなくてもよいが、含有する場合、酸捕捉剤の含有量は、組成物の全固形分を基準として、通常は0.001~10質量%であり、好ましくは0.01~5質量%である。 These acid scavengers may be used alone or in combination of two or more.
The composition according to the present invention may or may not contain an acid scavenger, but when it is contained, the content of the acid scavenger is usually 0.001 to 0 based on the total solid content of the composition. It is 10% by mass, preferably 0.01 to 5% by mass.
本発明の樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、界面活性剤、高級脂肪酸誘導体、熱重合開始剤、無機粒子、紫外線吸収剤、有機チタン化合物、酸化防止剤、凝集防止剤、フェノール系化合物、他の高分子化合物、可塑剤及びその他の助剤類(例えば、消泡剤、難燃剤など)等を配合することができる。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。これらの添加剤を配合する場合、その合計配合量は本発明の樹脂組成物の固形分の3質量%以下とすることが好ましい。 <Other additives>
The resin composition of the present invention comprises various additives such as a surfactant, a higher fatty acid derivative, a thermal polymerization initiator, an inorganic particle, and an ultraviolet absorber, if necessary, as long as the effects of the present invention can be obtained. Organic titanium compounds, antioxidants, antiaggregating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (eg, antifoaming agents, flame retardant agents, etc.) can be blended. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The descriptions of Nos. 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
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。 [Surfactant]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
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。
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
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。 The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
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。 Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
本発明の樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で本発明の樹脂組成物の表面に偏在させてもよい。 [Higher fatty acid derivative]
In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.
本発明の樹脂組成物は、熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。熱ラジカル重合開始剤を添加することによって樹脂及び重合性化合物の重合反応を進行させることもできるので、より耐溶剤性を向上できる。また、上述した光重合開始剤も熱により重合を開始する機能を有する場合があり、熱重合開始剤として添加することができる場合がある。 [Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, and may particularly contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be promoted by adding the thermal radical polymerization initiator, the solvent resistance can be further improved. Further, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
本発明の樹脂組成物は、無機微粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。 [Inorganic particles]
The resin composition of the present invention may contain inorganic fine particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
微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。 The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
The average particle size of the fine 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, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.
本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、p-オクチルフェニルサリシレート、p-t-ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-アミル-5’-イソブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-プロピルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-[2’-ヒドロキシ-5’-(1,1,3,3-テトラメチル)フェニル]ベンゾトリアゾールなどが挙げられる。 [UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、0.001質量%以上1質量%以下であることが好ましく、0.01質量%以上0.1質量%以下であることがより好ましい。 In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。 [Organic titanium compound]
The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
有機チタン化合物の具体例を、以下のI)~VII)に示す:
I)チタンキレート化合物:中でも、樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を2個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n-ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2-エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n-ノニロキサイド)、チタニウムテトラ(n-プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2-(アリロキシメチル)ブトキサイド}]等である。
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。 Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentangionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetoneate and the like.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。上述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物を使用することもでき、この内容は本明細書に組み込まれる。
また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。
潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
好ましい酸化防止剤の例としては、2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノールおよび式(3)で表される化合物が挙げられる。 〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6] -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification.
In addition, the composition of the present invention may contain a latent antioxidant, if necessary.
The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
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。 [Anti-coagulation agent]
The resin composition of the present embodiment may contain an anti-aggregation agent, if necessary. Examples of the antiaggregating agent include sodium polyacrylate and the like.
本発明の組成物は、凝集防止剤を含んでも含まなくてもよいが、含む場合、凝集防止剤の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上10質量%以下であることが好ましく、0.02質量%以上5質量%以下であることがより好ましい。 In the present invention, one type of anti-aggregation agent may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.
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。 [Phenolic compounds]
The resin composition of the present embodiment may contain a phenolic compound, if necessary. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP. BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (above, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.
本発明の組成物は、フェノール系化合物を含んでも含まなくてもよいが、含む場合、フェノール系化合物の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上30質量%以下であることが好ましく、0.02質量%以上20質量%以下であることがより好ましい。 In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.
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。 [Other polymer compounds]
Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acid, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.
本発明の組成物は、他の高分子化合物を含んでも含まなくてもよいが、含む場合、他の高分子化合物の含有量は、本発明の組成物の全固形分質量に対して、0.01質量%以上30質量%以下であることが好ましく、0.02質量%以上20質量%以下であることがより好ましい。 In the present invention, one type of other polymer compound may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
本発明の樹脂組成物の粘度は、樹脂組成物の固形分濃度により調整できる。塗布膜厚の観点から、1,000mm2/s~12,000mm2/sが好ましく、2,000mm2/s~10,000mm2/sがより好ましく、2,500mm2/s~8,000mm2/sが更に好ましい。上記範囲であれば、均一性の高い塗布膜を得ることが容易になる。1,000mm2/s以下では、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困難であり、12,000mm2/s以上では、塗布面状が悪化する可能性がある。 <Characteristics of resin composition>
The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 2,500 mm 2 / s to 8,000 mm. 2 / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film. At 1,000 mm 2 / s or less, it is difficult to apply the film with a film thickness required as an insulating film for rewiring, for example, and at 12,000 mm 2 / s or more, the coating surface condition may deteriorate. ..
本発明の樹脂組成物の含水率は、2.0質量%未満であることが好ましく、1.5質量%未満であることがより好ましく、1.0質量%未満であることが更に好ましい。2.0%以上では、樹脂組成物の保存安定性が損なわれる可能性がある。
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。 <Restrictions on substances contained in the resin composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is 2.0% or more, the storage stability of the resin composition may be impaired.
Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。 Considering the use as a semiconductor material, the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
本発明の樹脂組成物を硬化することにより、この樹脂組成物の硬化物を得ることができる。
本発明の硬化物は、本発明の樹脂組成物を硬化してなる硬化物である。
樹脂組成物の硬化は加熱によるものであることが好ましく、加熱温度が120℃~400℃の範囲内であることがより好ましく、140℃~380℃の範囲内にあることが更に好ましく、170℃~350℃の範囲内にあることが特に好ましい。樹脂組成物の硬化物の形態は、特に限定されず、フィルム状、棒状、球状、ペレット状など、用途に合わせて選択することができる。本発明において、この硬化物は、フィルム状であることが好ましい。また、樹脂組成物のパターン加工によって、壁面への保護膜の形成、導通のためのビアホール形成、インピーダンスや静電容量あるいは内部応力の調整、放熱機能付与など、用途にあわせて、この硬化物の形状を選択することもできる。この硬化物(硬化物からなる膜)の膜厚は、0.5μm以上150μm以下であることが好ましい。
本発明の樹脂組成物を硬化した際の収縮率は、50%以下が好ましく、45%以下がより好ましく、40%以下が更に好ましい。ここで、収縮率は、樹脂組成物の硬化前後の体積変化の百分率を指し、下記の式より算出することができる。
収縮率[%]=100-(硬化後の体積÷硬化前の体積)×100 <Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape. In the present invention, the cured product is preferably in the form of a film. In addition, by pattern processing of the resin composition, this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and providing heat dissipation function. You can also choose the shape. The film thickness of this cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less. Here, the shrinkage ratio refers to the percentage of the volume change of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage rate [%] = 100- (volume after curing ÷ volume before curing) x 100
本発明の樹脂組成物の硬化物のイミド化反応率は、70%以上が好ましく、80%以上がより好ましく、90%以上が更に好ましい。70%未満では硬化物の機械特性が劣る可能性がある。
本発明の樹脂組成物の硬化物の破断伸びは、30%以上が好ましく、40%以上がより好ましく、50%以上が更に好ましい。
本発明の樹脂組成物の硬化物のガラス転移温度(Tg)は、180℃以上であることが好ましく、210℃以上であることがより好ましく、230℃以上であることがさらに好ましい。 <Characteristics of cured product of resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be inferior.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.
本発明の樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
混合は撹拌羽による混合、ボールミルによる混合、タンク自身を回転させる混合などを採用することができる。
混合中の温度は10~30℃が好ましく、15~25℃がより好ましい。 <Preparation of resin composition>
The resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.
For mixing, mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like can be adopted.
The temperature during mixing is preferably 10 to 30 ° C, more preferably 15 to 25 ° C.
フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。
更にフィルターを用いたろ過後、ボトルに充填した樹脂組成物を減圧下に置き、脱気する工程を施しても良い。 Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the resin composition of the present invention. The filter hole diameter may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferable to use HDPE (high density polyethylene). The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Examples of the connection mode include a mode in which an HDPE filter having a hole diameter of 1 μm is connected in series as the first stage and an HDPE filter having a hole diameter of 0.2 μm is connected in series as the second stage. In addition, various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.5 MPa or less is more preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
Further, after filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure to perform a step of degassing.
4,4’-オキシジフタル酸二無水物(ODPA)155.1gを2リットル容量のセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)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)2 06.3g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(DADPE)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、ろ過により取り除き、反応液を得た。
得られた反応液を3リットルのエチルアルコールに加えて、粗ポリマーからなる沈殿物を生成した。生成した粗ポリマーを濾取し、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P-1を得た。
このポリマーP-1の重量平均分子量(Mw)を測定したところ、20,000であっ た。 <Synthesis Example 1: Synthesis of Polymer P-1>
155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a 2 liter volume separable flask and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer P-1.
The weight average molecular weight (Mw) of this polymer P-1 was measured and found to be 20,000.
合成例1において、4,4’-オキシジフタル酸二無水物155.1gに代えて、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物147.1gを用いた以外は、合成例1に記載の方法と同様にして反応を行うことにより、ポリマーP-2を得た。
このポリマーP-2の重量平均分子量(Mw)を測定したところ、22,000であった。 <Synthesis Example 2: Synthesis of Polymer P-2>
Synthesis Example 1 except that 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride. Polymer P-2 was obtained by carrying out the reaction in the same manner as in the method described in 1.
The weight average molecular weight (Mw) of this polymer P-2 was measured and found to be 22,000.
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸二無水物(4,4’-オキシジフタル酸を140℃で12時間乾燥したもの)と、18.6g(129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、10.7gのピリジンと、140gのダイグライム(ジエチレングリコールジメチルエーテル)とを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートとのジエステルを製造した。次いで、反応混合物を-10℃に冷却し、温度を-10±4℃に保ちながら、16.12g(135.5ミリモル)のSOCl2を10分かけて加えた。50mLのN-メチルピロリドンで希釈した後、反応混合物を室温で2時間撹拌した。次いで、100mLのN-メチルピロリドンに11.08g(58.7ミリモル)の4,4’-オキシジアニリンを溶解させた溶液を、20~23℃で20分かけて反応混合物に滴下した。次いで、反応混合物を室温で1晩撹拌した。次いで、5リットルの水に加えてポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5,000rpmの速度で15分間撹拌した。ポリイミド前駆体を濾取し、4リットルの水に加えて再度30分間撹拌し、再び濾取した。次いで、得られたポリイミド前駆体を減圧下、45℃で3日間乾燥し、ポリマーP-3を得た。
このポリマーP-3の重量平均分子量(Mw)を測定したところ、18,000であった。 <Synthesis Example 3: Synthesis of Polymer P-3>
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (4,4'-oxydiphthalic acid dried at 140 ° C. for 12 hours) and 18.6 g (129 mmol) of 2- Hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain 4,4'-oxydiphthalic acid. A diester with 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-oxydianiline in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated by adding to 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5,000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain a polymer P-3.
The weight average molecular weight (Mw) of this polymer P-3 was measured and found to be 18,000.
撹拌機、温度計、滴下漏斗、窒素導入管を備え付けたフラスコ内に、4,4′-ジアミノジフェニルエーテル 100.12部(0.5モル),N-メチル-2-ピロリドン736部を仕込み,窒素ガス雰囲気下で室温で撹拌し,溶解した後,冷却した。続いて,3,3′,4,4′-ベンゾフェノンテトラカルボン酸二無水物128.9部(0.4モル)、1,3-ビス(3,4-ジカルボキシフェニル)-1,1,3,3-テトラメチルジシロキサン二無水物42.65部(0.1モル)及びN-メチル-2-ピロリドン50.4部を仕込み、窒素ガス雰囲気下で反応温度30℃で酸成分が溶解するまで反応させ、さらに反応温度55℃で20時間加熱し、ポリイミド前駆体を得た。次に得られたポリイミド前駆体にイソシアナートエチルメタクリレート38.79部(0.25モル)を滴下漏斗より反応温度35℃で加え、10時間撹拌し、ポリマーP-4を得た。 <Synthesis Example 4: Synthesis of Polymer P-4>
In a flask equipped with a stirrer, a thermometer, a dropping funnel, and a nitrogen introduction tube, 100.12 parts (0.5 mol) of 4,4'-diaminodiphenyl ether and 736 parts of N-methyl-2-pyrrolidone were charged, and nitrogen was charged. The mixture was stirred at room temperature in a gas atmosphere, dissolved, and then cooled. Subsequently, 128.9 parts (0.4 mol) of 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,1 42.65 parts (0.1 mol) of 3,3-tetramethyldisiloxane dianhydride and 50.4 parts of N-methyl-2-pyrrolidone were charged, and the acid component was dissolved at a reaction temperature of 30 ° C. under a nitrogen gas atmosphere. The reaction was further carried out at a reaction temperature of 55 ° C. for 20 hours to obtain a polyimide precursor. Next, 38.79 parts (0.25 mol) of isocyanate ethyl methacrylate was added to the obtained polyimide precursor from a dropping funnel at a reaction temperature of 35 ° C., and the mixture was stirred for 10 hours to obtain a polymer P-4.
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、各感光性樹脂組成物を得た。また、比較例において、下記表に記載の成分を混合し、比較用組成物を得た。
具体的には、表に記載の成分の含有量は、表の「質量部」に記載の量とした。また、各組成物において、溶剤の含有量は、組成物の固形分濃度が表に記載の値となるようにした。
得られた感光性樹脂組成物及び比較用組成物を、フィルタ孔径が0.8μmのポリテトラフルオロエチレン製フィルターを通して加圧ろ過した。
また、表中、「-」の記載は該当する成分を組成物が含有していないことを示している。 <Examples and comparative examples>
In each example, the components listed in the table below were mixed to obtain each photosensitive resin composition. Further, in the comparative example, the components listed in the table below were mixed to obtain a comparative composition.
Specifically, the content of the component shown in the table is the amount described in "Mass part" of the table. Further, in each composition, the solvent content was adjusted so that the solid content concentration of the composition was the value shown in the table.
The obtained photosensitive resin composition and comparative composition were pressure-filtered through a polytetrafluoroethylene filter having a filter pore size of 0.8 μm.
Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.
・P-1~P-4:上記で合成したP-1~P-4 〔resin〕
-P-1 to P-4: P-1 to P-4 synthesized above
・M-1:テトラエチレングリコールジメタクリレート
・M-2:テトラエチレングリコールジアクリレート [Radical cross-linking agent]
-M-1: Tetraethylene glycol dimethacrylate-M-2: Tetraethylene glycol diacrylate
・I-1:Irgacure OXE-01(BASF社製)
・I-2:3,5-ビス(4-ジエチルアミノベンジリデン)-1-メチル-4-アザシクロヘキサノン
・I-3:Irgacure784(BASF社製) [Photopolymerization initiator]
-I-1: Irgure OXE-01 (manufactured by BASF)
-I-2: 3,5-bis (4-diethylaminobenzylidene) -1-methyl-4-azacyclohexanone-I-3: Irgacure784 (manufactured by BASF)
・A-1:WPBG-140(富士フイルム和光純薬株式会社製) [Base generator]
・ A-1: WPBG-140 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・B-1:4-メトキシフェノール
・B-2:2-ニトロソ-1-ナフト-ル [Polymerization inhibitor]
・ B-1: 4-methoxyphenol ・ B-2: 2-nitroso-1-naphthol
・C-1:KBM-503(信越シリコーン社製)
・C-2:N-(3-(トリエトキシシリル)プロピル)フタルアミド酸
・C-3:ベンゾフェノン-3,3’-ビス(N-(3-トリエトキシシリル)プロピルアミド)-4,4’-ジカルボン酸 〔Silane coupling agent〕
・ C-1: KBM-503 (manufactured by Shinetsu Silicone Co., Ltd.)
-C-2: N- (3- (triethoxysilyl) propyl) phthalamide acid-C-3: Benzophenone-3,3'-bis (N- (3-triethoxysilyl) propylamide) -4,4' -Dicarboxylic acid
・D-1:テトラゾール [Migration inhibitor]
・ D-1: Tetrazole
・J-1:N-フェニルジエタノールアミン
・J-2:N-(4-クロロフェニル)グリシン 〔Additive〕
-J-1: N-Phenyldiethanolamine-J-2: N- (4-chlorophenyl) glycine
・NMP:N-メチル-2-ピロリドン
・EL:乳酸エチル
・GBL:γ-ブチロラクトン
・DMSO:ジメチルスルホキシド
表中、「比率」の欄の記載は、溶剤の全質量に対する各溶剤の含有量(質量%)を示している。 〔solvent〕
-NMP: N-methyl-2-pyrrolidone-EL: Ethyl lactate-GBL: γ-butyrolactone-DMSO: Dimethyl sulfoxide In the table, the description in the "Ratio" column indicates the content (mass) of each solvent with respect to the total mass of the solvent. %) Is shown.
<破断伸び率の評価>
各実施例及び比較例において、それぞれ、各感光性樹脂組成物又は各比較用組成物を、シリコンウエハ上にスピンコート法により塗布した。感光性樹脂組成物層が塗布されたシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に20μmの厚さの均一な感光性樹脂組成物層を形成した。
シリコンウエハ上の感光性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、露光波長365nmで、500mJ/cm2の露光エネルギーでフォトマスクを用いて、パターン状(10mm×50mm)に露光した。
露光後、表の「現像液」の欄に記載の「溶剤」及び「塩基」を表に記載の質量部で混合して調製した現像液を、表の「供給方法」の欄に記載の供給方法により上記露光後の感光性樹脂組成物層に対して供給し、表に記載のリンス液で処理した。
シャワーと記載された例においては、シャワーノズルを用いて100ml/minで1分間現像液を供給した。
パドルと記載された例においては、ストレートノズルにて、現像液を100ml供給し、パドル現像を繰り返し2回実施した。
上記処理後、露光した感光性樹脂組成物(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表の「キュア温度(℃)」の欄に記載の温度に達した後、表の「キュア時間(min)」の欄に記載の時間において上記温度を維持した。硬化後の樹脂層を4.9質量%フッ化水素酸溶液に浸漬し、シリコンウエハから樹脂層を剥離し、樹脂層(硬化膜)を得た。
上記で得られた樹脂層(硬化膜)の破断伸び率を、以下の通り求めた。
まず、上記で剥離した樹脂層(硬化膜)を引張り試験機(テンシロン)を用いてクロスヘッドスピード300mm/分、としてフィルムの長手(長さ)方向、幅方向について、25℃、65%相対湿度(RH)の環境下にてJIS-K6251:2017に準拠して破断伸びを測定した。長手方向、幅方向それぞれの破断伸びの測定を各5回ずつ行った。長手方向と幅方向の破断伸び率の計10回の測定結果の算術平均値を破断伸び率の指標値とした。上記指標値(%)は表中の「破断伸び」の欄に記載した。破断伸び率の数値が高い方が好ましく、55%以上を合格とする。
また、「現像液」又は「リンス液」の欄に記載の略語の詳細は下記の通りである。
・NMP:N-メチル-2-ピロリドン
・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
・PGME:プロピレングリコールモノメチルエーテル
・TMAHaq:テトラメチルアンモニウムヒドロキシドの25質量%水溶液 (evaluation)
<Evaluation of elongation at break>
In each Example and Comparative Example, each photosensitive resin composition or each comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer.
The photosensitive resin composition layer on the silicon wafer is patterned (10 mm × 50 mm) using a stepper (Nikon NSR 2005 i9C) at an exposure wavelength of 365 nm and an exposure energy of 500 mJ / cm 2 using a photomask. Exposed.
After exposure, a developer prepared by mixing the "solvent" and "base" described in the "Developer" column of the table by the mass parts listed in the table is supplied as described in the "Supply method" column of the table. By the method, it was supplied to the photosensitive resin composition layer after the above exposure, and treated with the rinse solution shown in the table.
In the example described as shower, the developer was supplied at 100 ml / min for 1 minute using a shower nozzle.
In the example described as paddle, 100 ml of the developing solution was supplied by a straight nozzle, and paddle development was repeated twice.
After the above treatment, the exposed photosensitive resin composition (resin layer) is heated at a temperature rising rate of 10 ° C./min under a nitrogen atmosphere, and the temperature described in the "Cure temperature (° C.)" column of the table. After reaching the above temperature, the above temperature was maintained for the time described in the “Cure time (min)” column of the table. The cured resin layer was immersed in a 4.9 mass% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin layer (cured film).
The elongation at break of the resin layer (cured film) obtained above was determined as follows.
First, the resin layer (cured film) peeled off above is set to a crosshead speed of 300 mm / min using a tensile tester (Tencilon), and the film is 25 ° C. and 65% relative humidity in the longitudinal (length) direction and width direction. The elongation at break was measured in accordance with JIS-K6251: 2017 under the environment of (RH). The fracture elongation in each of the longitudinal direction and the width direction was measured 5 times each. The arithmetic mean value of the results of a total of 10 measurements of the breaking elongation in the longitudinal direction and the width direction was used as the index value of the breaking elongation. The above index value (%) is described in the column of "elongation at break" in the table. It is preferable that the numerical value of the elongation at break is high, and 55% or more is accepted.
The details of the abbreviations described in the columns of "developer" or "rinse" are as follows.
-NMP: N-methyl-2-pyrrolidone-PGMEA: Propylene glycol monomethyl ether acetate-PGME: Propylene glycol monomethyl ether-TMAHaq: 25% by mass aqueous solution of tetramethylammonium hydroxide
各実施例及び比較例において、それぞれ、各感光性樹脂組成物又は比較用組成物を、シリコンウエハ上にスピンコート法により塗布した。感光性樹脂組成物層が塗布されたシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に表の「膜厚(μm)」の欄に記載の厚さの均一な感光性樹脂組成物層を形成した。次いで、シリコンウエハ上の感光性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、露光波長365nmで、500mJ/cm2の露光エネルギーで露光し、露光した感光性樹脂組成物層(樹脂層)を、各現像液で60秒間シャワー現像、リンスを実施して、直径10μmのホールを形成した。次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表の「キュア温度(℃)」に記載の温度に達した後、表の「キュア時間(min)」に記載の時間加熱した。室温まで冷却後、樹脂層の表面に、再度、上記感光性樹脂組成物又は比較用組成物と同じ組成物を用いて、上記と同様に感光性樹脂組成物の塗布から、パターン化した膜の3時間加熱までの手順を再度実施して、樹脂層を2層有する積層体(1)を形成した。
〔積層体(2)の製造〕
上記で得られた積層体(1)の表面に、積層体(1)の製造に用いた感光性樹脂組成物又は比較用組成物と同じ組成物を用いて、積層体(1)の製造と同様の手順を再度実施することで、樹脂層を4層有する積層体(2)を作製した。
〔積層体(3)の製造〕
各実施例及び比較例において、それぞれ、各感光性樹脂組成物又は比較用組成物を、シリコンウエハ上にスピンコート法により塗布した。感光性樹脂組成物層が塗布されたシリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に表の「膜厚(μm)」の欄に記載の厚さの均一な感光性樹脂組成物層を形成した。シリコンウエハ上の感光性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで露光し、露光した感光性樹脂組成物層(樹脂層)を、各現像液で60秒間現像して、直径10μmのホールを形成した。次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表の「キュア温度(℃)」に記載の温度に達した後、表の「キュア時間(min)」に記載の時間加熱した。室温まで冷却後、上記ホール部分を覆うように、感光性樹脂組成物層の表面の一部に、蒸着法により厚さ2μmの銅薄層(金属層)を形成した。さらに、金属層及び感光性樹脂組成物層の表面に、再度、同じ感光性樹脂組成物又は比較用組成物を用いて、上記と同様に感光性樹脂組成物の塗布から、パターン化した膜の3時間加熱までの手順を再度実施して、樹脂層/金属層/樹脂層からなる積層体(3)を作製した。
〔積層体(4)の製造〕
上記積層体(3)の表面に、さらに、積層体(3)と同様の方法により、銅薄層(金属層)と樹脂層を交互に作製し、樹脂層/金属層/樹脂層/金属層/樹脂層/金属層/樹脂層からなる積層体(4)を作製した。 <Evaluation of peeling defects (adhesion between layers)>
In each Example and Comparative Example, each photosensitive resin composition or comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer is dried on a hot plate at 100 ° C. for 5 minutes, and the silicon wafer is exposed to a uniform thickness described in the “Film thickness (μm)” column of the table. A layer of the sex resin composition was formed. Next, the photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2 at an exposure wavelength of 365 nm using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer ( The resin layer) was shower-developed and rinsed with each developer for 60 seconds to form holes having a diameter of 10 μm. Then, in a nitrogen atmosphere, the temperature is raised at a heating rate of 10 ° C./min to reach the temperature described in "Cure temperature (° C.)" in the table, and then described in "Cure time (min)" in the table. Heated for hours. After cooling to room temperature, the surface of the resin layer is again coated with the same composition as the above-mentioned photosensitive resin composition or the comparative composition, and the photosensitive resin composition is applied in the same manner as above to obtain a patterned film. The procedure up to heating for 3 hours was carried out again to form a laminate (1) having two resin layers.
[Manufacturing of laminated body (2)]
The production of the laminate (1) and the production of the laminate (1) by using the same composition as the photosensitive resin composition or the comparative composition used for the production of the laminate (1) on the surface of the laminate (1) obtained above. By repeating the same procedure again, a laminate (2) having four resin layers was produced.
[Manufacturing of laminated body (3)]
In each Example and Comparative Example, each photosensitive resin composition or comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer is dried on a hot plate at 100 ° C. for 5 minutes, and the silicon wafer is exposed to a uniform thickness described in the “Film thickness (μm)” column of the table. A layer of the sex resin composition was formed. The photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was developed. It was developed with a solution for 60 seconds to form a hole having a diameter of 10 μm. Then, in a nitrogen atmosphere, the temperature is raised at a heating rate of 10 ° C./min to reach the temperature described in "Cure temperature (° C.)" in the table, and then described in "Cure time (min)" in the table. Heated for hours. After cooling to room temperature, a thin copper layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer so as to cover the hole portion. Further, the same photosensitive resin composition or comparative composition is used again on the surfaces of the metal layer and the photosensitive resin composition layer, and the photosensitive resin composition is applied to the surface of the patterned film in the same manner as described above. The procedure up to heating for 3 hours was carried out again to prepare a laminate (3) composed of a resin layer / metal layer / resin layer.
[Manufacturing of laminated body (4)]
Further, a thin copper layer (metal layer) and a resin layer are alternately formed on the surface of the laminate (3) by the same method as that of the laminate (3), and a resin layer / metal layer / resin layer / metal layer is formed. A laminate (4) composed of a / resin layer / metal layer / resin layer was produced.
上記で得られた各積層体を、空気中180℃で500時間加熱した。その後、各積層体の樹脂層面に対し、垂直方向に幅5mmとなるように、かつ、樹脂層と樹脂層が接している部分と、金属層と樹脂層が接している部分を、それぞれ、切り出した。その切り出した断面を観察して、1つの切り出し片における、樹脂層/樹脂層間、及び金属層/樹脂層間での剥がれの有無を光学顕微鏡で確認した。剥がれの発生は、樹脂層/樹脂層間、金属層/樹脂層間の剥がれのいずれであるかに関わらず全体での個数を確認した。評価は下記評価基準に従って行い、評価結果は表の「積層信頼性」の欄に記載した。剥がれの発生が少ないほど、優れた密着性を有していることを表し、好ましい結果となる。
-評価結果-
A:剥がれの発生なし
B:剥がれの発生が1~2個
C:剥がれの発生が3~5個
D:剥がれの発生が6個以上 [Evaluation of peeling defects (after heat treatment)]
Each laminate obtained above was heated in air at 180 ° C. for 500 hours. After that, the portion where the resin layer and the resin layer are in contact with each other and the portion where the metal layer and the resin layer are in contact are cut out so as to have a width of 5 mm in the vertical direction with respect to the resin layer surface of each laminate. rice field. By observing the cut-out cross section, the presence or absence of peeling between the resin layer / resin layer and the metal layer / resin layer in one cut piece was confirmed with an optical microscope. The total number of peeling was confirmed regardless of whether the peeling occurred between the resin layer / resin layer and the metal layer / resin layer. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Stacking reliability" column of the table. The less the occurrence of peeling, the better the adhesion, and the more preferable the result.
-Evaluation results-
A: No peeling occurred B: 1 to 2 peeling occurred C: 3 to 5 peeling occurred D: 6 or more peeling occurred
実施例1において使用した感光性樹脂組成物を、表面に銅薄層が形成された樹脂基材の銅薄層の表面にスピンコート法により層状に適用して、100℃で4分間乾燥し、膜厚20μmの感光性樹脂組成物層を形成した後、ステッパー((株)ニコン製、NSR1505 i6)を用いて露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が10μmであるバイナリマスク)を介して、波長365nmで行った。露光後、100℃で4分間加熱した。上記加熱後、実施例1で用いた現像液で現像し、実施例1で用いたリンス液でリンスして、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、120分間維持して層を硬化し、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。
また、これらの再配線層用層間絶縁膜を使用して電子デバイスを製造したところ、問題なく動作することを確認した。 <Example 101>
The photosensitive resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a photosensitive resin composition layer having a thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes. After the above heating, it was developed with the developer used in Example 1 and rinsed with the rinse solution used in Example 1 to obtain a layer pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 180 ° C., the layer was cured by maintaining for 120 minutes to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
In addition, when an electronic device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the electronic device operated without any problem.
Claims (9)
- 下記式(2)で表される繰り返し単位を有するポリイミド前駆体、及び、光重合開始剤を含む感光性樹脂組成物を基材上に適用して膜を形成する膜形成工程、
前記膜を選択的に露光する露光工程、
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、並びに、
前記現像により得られたパターンを加熱する加熱工程を含み、
前記現像液の全質量に対する水の含有量が50質量%以下である、
硬化物の製造方法。
An exposure process that selectively exposes the film,
A developing step of developing the film after exposure to form a pattern with a developing solution containing at least one compound selected from the group consisting of bases and base generators, and
Including a heating step of heating the pattern obtained by the development.
The content of water with respect to the total mass of the developer is 50% by mass or less.
A method for manufacturing a cured product.
- 前記現像液が、前記塩基として、有機塩基を含む、請求項1に記載の硬化物の製造方法。 The method for producing a cured product according to claim 1, wherein the developer contains an organic base as the base.
- 前記加熱工程が、加熱により、前記塩基、及び、前記塩基発生剤から発生した塩基よりなる群から選ばれた少なくとも1種の化合物の作用により、前記パターン内で前記ポリイミド前駆体のイミド化を促進する工程である、請求項1又は2に記載の硬化物の製造方法。 The heating step promotes imidization of the polyimide precursor in the pattern by the action of at least one compound selected from the group consisting of the base and the base generated from the base generator by heating. The method for producing a cured product according to claim 1 or 2, which is a step thereof.
- 前記加熱工程における加熱の温度が、120~230℃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。 The method for producing a cured product according to any one of claims 1 to 3, wherein the heating temperature in the heating step is 120 to 230 ° C.
- 前記現像工程が、前記現像液を前記露光後の膜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、請求項1~4のいずれか1項に記載の硬化物の製造方法。 The method for producing a cured product according to any one of claims 1 to 4, wherein the developing step is a step of supplying the developing solution to the exposed film by a shower or continuously supplying the developing solution.
- 前記現像工程における現像がネガ型現像である、請求項1~5のいずれか1項に記載の硬化物の製造方法。 The method for producing a cured product according to any one of claims 1 to 5, wherein the development in the development step is negative type development.
- 請求項1~6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、積層体の製造方法。 A method for producing a laminated body, wherein the method for producing a cured product according to any one of claims 1 to 6 is repeated a plurality of times.
- 前記複数回行われる硬化物の製造方法の間に、硬化物上に金属層を形成する金属層形成工程を更に含む、請求項7に記載の積層体の製造方法。 The method for producing a laminate according to claim 7, further comprising a metal layer forming step of forming a metal layer on the cured product during the method for producing the cured product which is performed a plurality of times.
- 請求項1~6のいずれか1項に記載の硬化物の製造方法、又は、請求項7若しくは8に記載の積層体の製造方法を含む、電子デバイスの製造方法。 A method for manufacturing an electronic device, which comprises the method for manufacturing a cured product according to any one of claims 1 to 6, or the method for manufacturing a laminate according to claim 7 or 8.
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