CN114402256A - Organic film, method for producing same, composition, laminate, and semiconductor device - Google Patents

Organic film, method for producing same, composition, laminate, and semiconductor device Download PDF

Info

Publication number
CN114402256A
CN114402256A CN202080063592.5A CN202080063592A CN114402256A CN 114402256 A CN114402256 A CN 114402256A CN 202080063592 A CN202080063592 A CN 202080063592A CN 114402256 A CN114402256 A CN 114402256A
Authority
CN
China
Prior art keywords
bis
group
formula
cyclopentadienyl
titanium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202080063592.5A
Other languages
Chinese (zh)
Inventor
室祐继
松井高史
青岛俊荣
岛田和人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN114402256A publication Critical patent/CN114402256A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • 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
    • 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
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/5329—Insulating materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The present invention provides an organic film having excellent solvent resistance, which satisfies at least 1 formula selected from the following formulae (1) and (2), formula (1), a method for producing the same, a composition for forming the organic film, a laminate including the organic film, and a semiconductor device including the organic film or the laminate: I/A is more than or equal to 2.5; formula (2): I/B is more than or equal to 0.5; in the formula (1) or the formula (2), I is q
Figure DDA0003538521090000014
In the range of (a) is a maximum value of a relative intensity value when neutron small angle scattering measurement is performed on the organic film, and A is q is
Figure DDA0003538521090000011
B is q is within a range of
Figure DDA0003538521090000012

Description

Organic film, method for producing same, composition, laminate, and semiconductor device
Technical Field
The invention relates to an organic film, a method for manufacturing the same, a composition, a laminate, and a semiconductor device.
Background
The organic film can be formed by an easy film formation method such as a coating method, a printing method, or a transfer method. Further, by adjusting the structure of each component (for example, resin or the like) contained in the film, the content of each component contained in the film, or the like, it is also possible to easily design the mechanical properties such as the breaking elongation of the film, the physical properties such as the insulating properties of the film, or the like. Therefore, in recent years, organic films containing organic materials have been used in various fields as films for devices used for various applications.
For example, organic films made of resins such as polyimide and benzoxazole are suitable for various applications because of their excellent heat resistance and insulating properties. The above-mentioned application is not particularly limited, but an example of the application is an application as an insulating film, a material for a sealing material, or a protective film when a semiconductor device for mounting is used. Further, the film can be used as a base film, a cover layer, or the like of a flexible substrate.
Such an organic film is expected to be industrially applied.
For example, patent document 1 describes a photosensitive resin composition containing a component (a) which is a photosensitive polyimide precursor and a component (B) having a specific structure.
Prior art documents
Patent document
Patent document 1: international publication No. 2017/033833
Disclosure of Invention
Technical problem to be solved by the invention
As an organic film is used in various fields, it is desired to provide an organic film excellent in solvent resistance.
An object of the present invention is to provide an organic film having excellent solvent resistance, a method for producing the same, a composition for forming the organic film, a laminate comprising the organic film, and a semiconductor device comprising the organic film or the laminate.
Means for solving the technical problem
Hereinafter, examples of representative embodiments of the present invention will be described.
< 1 > an organic film satisfying at least 1 formula selected from the following formula (1) and the following formula (2),
formula (1): I/A is more than or equal to 2.5;
formula (2): I/B is more than or equal to 0.5;
in the formula (1) or the formula (2), I is q
Figure BDA0003538521080000021
In the range ofThe maximum value of the relative intensity value when the neutron small angle scattering measurement is carried out on the organic film, wherein A is q
Figure BDA0003538521080000022
In the range of (a) and (B) is q, the minimum value of the relative intensity values in the measurement of neutron small angle scattering of the organic film
Figure BDA0003538521080000023
In the above range, Q is a value defined by the following formula (Q) in small angle scattering,
formula (Q): q ═ 4 pi/λ sin θ;
in the formula (Q), λ is the wavelength of the neutron beam, and θ is the scattering angle of the neutron beam.
< 2 > the organic film according to < 1 > which is a cured product of a coating film of a composition comprising at least 1 resin selected from the group consisting of polyimide, polybenzoxazole, a polyimide precursor and a polybenzoxazole precursor.
< 3 > the organic film according to < 2 >, wherein the above composition comprises a photosensitizer.
< 4 > a composition for use in the formation of an organic film as described in any one of < 1 > to < 3 >.
< 5 > a laminate comprising 2 or more layers of the organic film described in any one of < 1 > to < 3 > and comprising a metal layer between any of the above organic films.
< 6 > a semiconductor device comprising the organic film of any one of < 1 > to < 3 > or < 5 > the laminate.
< 7 > A method for producing an organic film, which comprises a film-forming step of forming a film by applying a composition to a substrate, wherein the organic film is produced according to any one of < 1 > to < 3 >.
< 8 > the method for producing an organic film < 7 > comprising a step of heating the film at 50 to 450 ℃.
Effects of the invention
According to the present invention, there are provided an organic film having excellent solvent resistance, a method for producing the same, a composition for forming the organic film, a laminate comprising the organic film, and a semiconductor device comprising the organic film or the laminate.
Detailed Description
Hereinafter, a main embodiment of the present invention will be described. However, the present invention is not limited to the embodiments shown.
In the present specification, a numerical range denoted by a symbol "to" means a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value, respectively.
In the present specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the desired action of the step can be achieved.
In the labeling of a group (atomic group) in the present specification, a label which is not labeled with a substitution and a substitution includes a group (atomic group) having no substituent and also includes a group (atomic group) having a substituent. For example, "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).
In the present specification, the term "exposure" includes not only exposure using light but also exposure using a particle beam such as an electron beam or an ion beam unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams, which are represented by the bright line spectrum of a mercury lamp or an excimer laser.
In the present specification, "(meth) acrylate" means both or either of "acrylate" and "methyl acrylate", "(meth) acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth) acryl" means both or either of "acryl" and "methacryl".
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of the components excluding the solvent from all the components of the composition. In the present specification, the solid content concentration refers to the percentage of the mass of the other components except the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values by gel permeation chromatography (GPC measurement), unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION), for example, as columns. The molecular weights of these were measured using THF (tetrahydrofuran) as an eluent unless otherwise specified. In addition, as for the detection in the GPC measurement, a detector having a wavelength of UV rays (ultraviolet rays) of 254nm is used unless otherwise specified.
In the present specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower", the layer may have another layer on the upper side or the lower side of the reference layer among the plurality of layers of interest. That is, the 3 rd layer or the element may be further interposed between the layer as the reference and the other layer, and the layer as the reference and the other layer do not need to be in contact. Unless otherwise specified, the direction in which the layers are stacked on the substrate stack is referred to as "up", or, in the case of having a composition layer, the direction from the substrate toward the composition layer is referred to as "up", and the opposite direction is referred to as "down". Note that, in this specification, such vertical direction setting is for convenience, and in an actual form, the "up" direction in this specification may be different from the vertical up direction.
In the present specification, unless otherwise specified, the composition may contain 2 or more compounds corresponding to each component contained in the composition. Unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ℃ and the atmospheric pressure is 101,325Pa (1 atm).
In the present specification, a combination of preferred embodiments is a more preferred embodiment.
(organic film)
The organic film of the present invention satisfies at least 1 formula selected from the following formulas (1) and (2).
Formula (1): I/A is more than or equal to 2.5;
formula (2): I/B is more than or equal to 0.5;
in the formula (1) or the formula (2), I is q
Figure BDA0003538521080000041
In the range of (a) is q, the maximum value of the relative intensity value in the measurement of neutron small angle scattering of the organic film
Figure BDA0003538521080000042
In the range of (a) and (B) is q, the minimum value of the relative intensity values in the measurement of neutron small angle scattering of the organic film
Figure BDA0003538521080000043
And Q is a value defined by the following formula (Q) in small angle scattering.
Formula (Q): q ═ 4 pi/λ sin θ;
in the formula (Q), λ is the wavelength of the neutron beam
Figure BDA0003538521080000051
θ is the scattering angle (°) of the neutron beam.
And the number of the first and second electrodes,
Figure BDA0003538521080000052
is 0.1 nm.
The organic film of the present invention is excellent in solvent resistance.
According to the present invention, it is considered to provide an organic film having excellent solvent resistance, in which solubility in a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP) is suppressed.
The organic film having excellent solvent resistance is considered useful because it is suppressed in dissolution in a solvent even when used for products and the like which may come into contact with the solvent at the time of use, storage, production, and the like, when a composition containing the solvent is further applied to the organic film, when a film formed on the organic film is subjected to solvent development, and the like.
The reason why the organic film of the present invention is excellent in solvent resistance is not clear, but is presumed as follows.
Satisfying formula (1) means that q is in
Figure BDA0003538521080000053
In the range of (a) and (b) is the minimum value A of the relative intensity values when neutron small angle scattering measurement is performed, q is in
Figure BDA0003538521080000054
The maximum value I of the relative intensity value when neutron small angle scattering measurement is performed in the range of (2) or more.
The satisfaction of the formula (2) means that q is in
Figure BDA0003538521080000055
The minimum value B of the relative intensity values when neutron small angle scattering measurement is performed in the range of (1), and the maximum value I is 0.5 times or more.
As a result of intensive studies, the present inventors found that q is
Figure BDA0003538521080000056
The maximum value I in the range of (1) is 2.5 times or more the minimum value a, or 0.5 times or more the minimum value B, or both of them are satisfied, and the organic film is excellent in solvent resistance.
Here, it is considered that q is in
Figure BDA0003538521080000057
The maximum value I of the relative intensity values when neutron small angle scattering measurement is performed in the range of (a) is a value that changes depending on the arrangement state, association state, and the like of components such as resin contained in the organic film.
For example, in the case where the organic film contains a resin having a ring structure (for example, a heterocyclic structure) such as a polyimide resin, for example, if the organic film contains a large number of stacked ring structures, the maximum value I is increased, and it is considered that at least 1 selected from the formulas (1) and (2) is satisfied.
Further, for example, if the organic film contains a large number of stacked ring structures, the interaction between the resins is strong, or the density of the resin in the organic film varies, and it is considered that the organic film has excellent solvent resistance because of the presence of a portion having a high resin density in the organic film.
From the above findings, the present inventors have found that an organic film having excellent solvent resistance can be obtained by satisfying at least 1 formula selected from the group consisting of the formula (1) and the formula (2), and have completed the present invention.
Further, for the reason of the interaction between the resins, it is considered that when the organic film satisfies at least 1 formula selected from the group consisting of the formula (1) and the formula (2), the organic film having a large elongation at break and excellent mechanical properties can be easily obtained.
< neutron Small Angle scattering (SANS) assay >
The neutron small angle scattering measurement was performed by the method described in the examples described below.
The relative intensity value in the present invention is a value obtained by measuring a neutron small angle scattering of a measurement sample and subtracting a background count measured using a blank cell (for example, an empty sample holder not filled with the measurement sample) in which the measurement sample is not placed from the measured count.
The organic film of the present invention may satisfy at least 1 formula selected from the group consisting of the formula (1) and the formula (2), but it is also one of preferable embodiments to satisfy both the formula (1) and the formula (2).
〔I/A〕
The value of I/a in formula (1) is 2.5 or more, preferably 2.6 or more, more preferably 2.7 or more, further preferably 2.8 or more, further preferably 3.0 or more, particularly preferably 4.0 or more, and most preferably 4.2 or more.
The upper limit of the value of I/a is not particularly limited, but may be, for example, 100 or less.
The value of I/a is determined, for example, by the structure of the resin contained in the organic film, the structure of the component other than the resin contained in the organic film, the combination of components having a specific structure, the content of each component contained in the organic film, the method for producing the organic film (for example, curing method), the thickness of the organic film, the type of the substrate on which the organic film is formed, and the like.
〔I/B〕
The value of I/B in formula (2) is 0.5 or more, preferably 0.55 or more, more preferably 0.60 or more, further preferably 0.65 or more, further preferably 0.70 or more, particularly preferably 0.80 or more, and most preferably 0.84 or more.
The upper limit of the value of I/B is not particularly limited, but may be, for example, 20 or less.
The value of I/B is determined, for example, by the structure of the resin contained in the organic film, the structure of the component other than the resin contained in the organic film, the combination of components having a specific structure, the content of each component contained in the organic film, the method for producing the organic film (for example, curing method), the thickness of the organic film, the type of the substrate on which the organic film is formed, and the like.
[ maximum value I ]
With respect to q is in
Figure BDA0003538521080000071
Is within the range of (1), provided that q is
Figure BDA0003538521080000072
Figure BDA0003538521080000073
May be present, but is preferably q in
Figure BDA0003538521080000074
In the above range, the maximum value of I, more preferably q, is
Figure BDA0003538521080000075
Within the above-mentioned range of the maximum value I.
〔I12/A、I13/A〕
When the organic film of the present invention satisfies formula (1), it preferably further satisfies formula (1-2) below, and more preferably further satisfies formula (1-3) below.
Formula (1-2): i is12/A≥2.5
Formula (1-3): i is13/A≥2.5
In the above formula (1-2) or the above formula (1-3), I12Is represented by q is
Figure BDA0003538521080000076
The maximum value of the relative intensity value when neutron small angle scattering measurement is performed on the organic film in the range of (1), I13Is represented by q is
Figure BDA0003538521080000077
The maximum value of the relative intensity values when the organic film is subjected to neutron small angle scattering measurement in the range of (2), wherein A and q are the same as those in the formula (1).
〔I22/B、I23/B〕
When the organic film of the present invention satisfies formula (2), it preferably further satisfies formula (2-2) below, and more preferably further satisfies formula (2-3) below.
Formula (2-2): i is22/B≥0.5
Formula (2-3): i is23/B≥0.5
In the above formula (1-2) or the above formula (1-3), I22Is represented by q is
Figure BDA0003538521080000078
The maximum value of the relative intensity value when neutron small angle scattering measurement is performed on the organic film in the range of (1), I23Is represented by q is
Figure BDA0003538521080000079
In the above range, B and q are the same as a and q in the formula (2).
< ingredient >
The organic film of the present invention may be any film containing an organic component, but is preferably a film containing a resin.
The resin is preferably a resin having a ring structure, and more preferably a resin having a heterocyclic structure.
The resin is not particularly limited, and examples thereof include polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, polysiloxane, a resin containing a siloxane structure, an epoxy resin, a (meth) acrylic resin, an olefin resin such as polyethylene or polypropylene, a vinyl resin such as polyvinyl chloride or polyvinyl ester, a fluorine resin such as polyurethane, polyurea, polyamide, polycarbonate, polyester, polystyrene, polyacetal, cellulose resin, phenol resin, and polytetrafluoroethylene.
Among these, the organic film preferably contains polyimide or polybenzoxazole as the resin, and more preferably contains polyimide, from the viewpoint of insulation properties and heat resistance of the organic film.
The polyimide or polybenzoxazole is preferably a polyimide contained in a composition described later, a polybenzoxazole contained in a composition described later, a polyimide formed from a polyimide precursor contained in a composition described later, or a polybenzoxazole formed from a polybenzoxazole precursor contained in a composition described later.
The organic film may further contain, as other components, each component contained in the composition described later. For example, when the organic film is formed as a cured product or the like and at least 1 component of the components in the composition is reacted to obtain the organic film, the components (e.g., photopolymerization initiator, polymerizable compound, and the like) included in the composition described later may be included in a form after the reaction (e.g., photopolymerization initiator after exposure, polymerizable compound after polymerization, and the like).
The organic film is preferably an organic film formed from a coating film of the composition, more preferably a cured product of a coating film of the composition, even more preferably a cured product of a coating film of the composition containing the above-mentioned resin, and particularly preferably a cured product of a coating film of a composition containing at least 1 resin (hereinafter, also referred to as "specific resin") selected from the group consisting of polyimide, polybenzoxazole, a polyimide precursor, and a polybenzoxazole precursor.
Hereinafter, each component contained in the composition will be described.
< resin >
The resin contained in the composition may be a resin contained in the organic film or a resin which becomes a resin contained in the organic film in a cured product, but is preferably at least 1 resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole and a polybenzoxazole precursor, more preferably at least 1 resin selected from the group consisting of polyimide and a polyimide precursor, and still more preferably a polyimide precursor.
[ polyimide precursor ]
The polyimide precursor used in the present invention is not particularly limited in kind and the like, but preferably contains a repeating unit represented by the following formula (2).
Formula (2)
[ chemical formula 1]
Figure BDA0003538521080000081
In the formula (2), A1And A2Each independently represents an oxygen atom or NH, R111Represents an organic radical having a valence of 2, R115Represents an organic group having a valence of 4, R113And R114Each independently represents a hydrogen atom or a 1-valent organic group.
A in the formula (2)1And A2Each independently represents an oxygen atom or NH, preferably an oxygen atom.
R in the formula (2)111Represents an organic group having a valence of 2. Examples of the 2-valent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, preferably a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, a group represented by-Ar-L-Ar-can be exemplified. Wherein Ar is independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-or NHCO-or a group consisting of a combination of 2 or more of the above. Preferred ranges of these are as described above.
R111Preferably derived from a diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. Only 1 kind of diamine may be used, or 2 or more kinds may be used.
Specifically, the diamine is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following.
[ chemical formula 2]
Figure BDA0003538521080000091
Wherein A is preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (-O) -, -S-, -SO2-, NHCO-or a combination of these, more preferably a single bond, selected from carbon atoms which may be substituted by fluorine atomsAn alkylene group having a number of 1 to 3, -O-, -C (═ O) -, -S-or-SO-2The group of-is further preferably-CH2-、-O-、-S-、-SO2-、-C(CF3)2-or-C (CH)3)2-。
Specific examples of the diamine include those selected from the group consisting of 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-or 1, 4-diaminocyclohexane, 1, 2-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane and isophoronediamine; m-or p-phenylenediamine, diaminotoluene, 4 '-diaminobiphenyl or 3, 3' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -diaminodiphenylmethane and 3,3 '-diaminodiphenylmethane, 4' -diaminodiphenylsulfone and 3,3 '-diaminodiphenylsulfone, 4' -diaminodiphenylsulfide and 3,3 '-diaminodiphenylsulfide, 4' -diaminobenzophenone or 3,3 '-diaminobenzophenone, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dimethoxy-4, 4 ' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4 ' -diaminop-terphenyl, 4 ' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis (4-aminophenoxy) phenyl ] sulfone, Bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3 ' -dimethyl-4, 4 ' -diaminodiphenylsulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3 ' -diethyl-4, 4 ' -diaminodiphenylmethane, 3 ' -dimethyl-4, 4 ' -diaminodiphenylmethane, 4 ' -diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, methyl ether, ethyl ether, methyl ether, ethyl ether, 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3 ', 4,4 ' -tetraaminobiphenyl, 3 ', 4,4 ' -tetraaminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4 ' -diaminobiphenyl, 9 ' -bis (4-aminophenyl) fluorene, 4,4 ' -dimethyl-3, 3 ' -diaminodiphenylsulfone, 3 ', 5,5 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane, 2, 4-diaminocumene and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, Acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, an ester of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecafluoroheptane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4 '-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4 '-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, at least 1 diamine selected from 2, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3 ', 5,5 ' -tetramethyl-4, 4 ' -diaminobiphenyl, 4 ' -diamino-2, 2 ' -bis (trifluoromethyl) biphenyl, 2 ', 5,5 ', 6,6 ' -hexafluorotolidine and 4,4 ' -diaminotetrabiphenyl.
Also, the following diamines (DA-1) to (DA-18) are preferred.
[ chemical formula 3]
Figure BDA0003538521080000121
[ chemical formula 4]
Figure BDA0003538521080000131
Further, a diamine having at least 2 alkylene glycol units in the main chain is also cited as a preferable example. More preferably, the diamine contains 2 or more ethylene glycol chains or propylene glycol chains in total or both of them in one molecule, and still more preferably a diamine containing no aromatic ring. Specific examples thereof include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, but the present invention is not limited thereto.
The following shows the structures of JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176.
[ chemical formula 5]
Figure BDA0003538521080000141
In the above, x, y and z are average values.
From the viewpoint of flexibility of the obtained organic film, R111Preferably represented by-Ar-L-Ar-. Wherein Ar is independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-or NHCO-or a group consisting of a combination of 2 or more of the above. Ar is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group of 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or SO2-. The aliphatic hydrocarbon group herein is preferably an alkylene group.
And, from the viewpoint of i-ray transmittance, R111Preferably a 2-valent organic compound represented by the following formula (51) or formula (61)And (4) a base. In particular, from the viewpoint of i-ray transmittance and ready availability, a 2-valent organic group represented by formula (61) is more preferable.
Formula (51)
[ chemical formula 6]
Figure BDA0003538521080000142
In the formula (51), R50～R57Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R50～R57At least 1 of them is a fluorine atom, a methyl group or a trifluoromethyl group.
As R50～R57Examples of the 1-valent organic group in (1) include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.
[ chemical formula 7]
Figure BDA0003538521080000151
In the formula (61), R58And R59Each independently a fluorine atom or a trifluoromethyl group.
Examples of the diamine compound to which the structure of formula (51) or (61) is imparted include 2,2 '-dimethylbenzidine, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4, 4' -diaminooctafluorobiphenyl. These may be used in 1 kind or 2 or more kinds may be used in combination.
R in the formula (2)115Represents a 4-valent organic group. The organic group having a valence of 4 is preferably an organic group having a valence of 4 comprising an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).
Formula (5)
[ chemical formula 8]
Figure BDA0003538521080000152
In the formula (5), R112Preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-and NHCO-and combinations thereof, more preferably a single bond or a group selected from C1-3 alkylene groups which may be substituted with fluorine atoms, -O-, -CO-, -S-and-SO2The group of (E) is more preferably selected from the group consisting of-CH2-、-C(CF3)2-、-C(CH3)2-, -O-, -CO-, -S and SO2-2-valent radical in (a).
Formula (6)
[ chemical formula 9]
Figure BDA0003538521080000153
With respect to R115Specific examples thereof include tetracarboxylic acid residues remaining after removing anhydride groups from tetracarboxylic acid dianhydrides. Only 1 kind of tetracarboxylic dianhydride may be used, or 2 or more kinds may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Formula (O)
[ chemical formula 10]
Figure BDA0003538521080000161
In the formula (O), R115Represents a 4-valent organic group. R115With R in the formula (2)115The meaning is the same, and the preferred range is the same.
Specific examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride (PMDA), 3,3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenyl sulfide tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenyl sulfone tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylmethane tetracarboxylic acid dianhydride, 2 ', 3,3 ' -diphenylmethane tetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 4,4 ' -oxydiphthalic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 1,4,5, 7-naphthalenetetracarboxylic acid dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 3,4, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,8,9, 10-phenanthrenetetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, and alkyl and alkoxy derivatives having 1 to 6 carbon atoms.
Further, as preferable examples, the following tetracarboxylic dianhydrides (DAA-1) to (DAA-5) can be cited.
[ chemical formula 11]
Figure BDA0003538521080000171
R111And R115At least one of them also preferably has an OH group. More specifically, as R111Examples thereof include residues of bisaminophenol derivatives.
R113And R114Each independently represents a hydrogen atom or a 1-valent organic group, R113And R114At least one of them preferably contains a polymerizable group, and more preferably both contain a polymerizable group. The polymerizable group is preferably a group capable of undergoing a crosslinking reaction by the action of heat, a radical, or the like, and is preferably a photo-radical polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a hydroxymethyl group, and an amino group. The radical polymerizable group contained in the polyimide precursor or the like is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III) is preferable.
[ chemical formula 12]
Figure BDA0003538521080000172
In the formula (III), R200Represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
In the formula (III), R201An alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-or a polyalkyleneoxy group.
As R201Preferable examples of the group include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene and-CH2CH(OH)CH2-, polyalkyleneoxy group, more preferably ethylene, propylene, trimethylene, -CH2CH(OH)CH2The polyalkyleneoxy group is more preferably a polyalkyleneoxy group, from the viewpoint that the formula (1) or the formula (2) is easily satisfied in the organic film.
In the present invention, a polyalkyleneoxy group means a group in which 2 or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group includes a plurality of alkyleneoxy groups having different alkylenes, the alkyleneoxy groups in the polyalkyleneoxy group may be arranged randomly, may be arranged in a block, or may be arranged in a pattern such as an alternating pattern.
The number of carbon atoms of the alkylene group (the number of carbon atoms including a substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent. Preferable substituents include alkyl groups, aryl groups, halogen atoms, and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.
The polyalkyleneoxy group is preferably a group in which a plurality of polyethyleneoxy groups, polypropyleneoxy groups, polytrimethyleneoxy groups, polytetramethyleneoxy groups, or polyethyleneoxy groups and a plurality of propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and still more preferably a polyethyleneoxy group, from the viewpoint of solvent solubility and solvent resistance. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as an alternating pattern. Preferred modes of repeating the number of ethyleneoxy groups and the like in these groups are as described above.
R113And R114Each independently a hydrogen atom or a 1-valent organic group. Examples of the organic group having a valence of 1 include aromatic groups and aralkyl groups in which an acidic group is bonded to 1,2 or 3 carbon atoms, preferably 1 carbon atom, constituting the aryl group. Specifically, the aromatic group has 6 to 20 carbon atoms and has an acidic group, and the aralkyl group has 7 to 25 carbon atoms and has an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably an OH group.
R113Or R114Also more preferred are a hydrogen atom, 2-hydroxybenzyl group, 3-hydroxybenzyl group and 4-hydroxybenzyl group.
From the viewpoint of solubility in organic solvents, R113Or R114Preferably an organic group having a valence of 1. The organic group having a valence of 1 preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms in the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched, or cyclic. Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, a 2-ethylhexyl 2- (2- (2-methoxyethoxy) ethoxy group, a 2- (2- (2-ethoxyethoxy) ethoxy group, a 2- (2- (2- (2-methoxyethoxy) ethoxy group, and a 2- (2- (2-ethoxyethoxy) ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group, and may be a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, bornyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphoroyl, dicyclohexyl, and sterenyl. Among these, cyclohexyl is most preferable from the viewpoint of achieving high sensitivity. The alkyl group substituted with an aromatic group is preferably a straight-chain alkyl group substituted with an aromatic group described later.
The aromatic group is specifically a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, benzodiindene ring, perylene ring, pentacene ring, ethanenaphthalene ring, phenanthrene ring, anthracene ring, tetracene ring, naphthalene ring, perylene ring, heptalene ring, perylene ring, pentalene ring, phenanthrene ring, anthracene ring, tetracene ring, perylene ring, phenanthrene ring, perylene ring, or the like,
Figure BDA0003538521080000191
A ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline (quinoxaline) ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline (phenanthroline) ring, a thiane ring, a benzopyran (chromene) ring, a xanthene (xanthene) ring, a phenoxathiine (phenoxathiine) ring, a phenothiazine (phenothiazine) ring or a phenazine (phenazine) ring. Benzene rings are most preferred.
In the formula (2), in R113In the case of a hydrogen atom or R114In the case of a hydrogen atom, the polyimide precursor may form a salt with a tertiary amine compound having an ethylenically unsaturated bond as a counter salt. As suchExamples of the tertiary amine compound having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
Also, the polyimide precursor preferably has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
In addition, in order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-a). That is, at least 1 kind of the polyimide precursor and the like used in the present invention is preferably a precursor having a repeating unit represented by the formula (2-a). With such a configuration, the width of the exposure latitude can be further increased.
Formula (2-A)
[ chemical formula 13]
Figure BDA0003538521080000201
In the formula (2-A), A1And A2Represents an oxygen atom, R111And R112Each independently represents a 2-valent organic group, R113And R114Each independently represents a hydrogen atom or a 1-valent organic group, R113And R114At least one of them is a group containing a polymerizable group, and preferably both are polymerizable groups.
A1、A2、R111、R113And R114Independently of A in formula (2)1、A2、R111、R113And R114The meaning is the same, and the preferred range is the same.
R112And R in the formula (5)112The meaning is the same, and the preferred range is the same.
The polyimide precursor may contain 1 repeating structural unit represented by formula (2), but may also contain 2 or more. Further, structural isomers of the repeating unit represented by the formula (2) may be contained. It is needless to say that the polyimide precursor may contain other kinds of repeating structural units in addition to the repeating unit of the formula (2).
As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all the repeating units are repeating units represented by the formula (2) can be exemplified.
The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. When the composition for forming an organic film of the present invention contains a compound containing a metal element, a preferred embodiment is one having a weight average molecular weight (Mw) of 22,000 to 26,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. When the composition for forming an organic film of the present invention contains a compound containing a metal element, a mode having a number average molecular weight (Mn) of 7,200 to 20,000 is also preferably used, and in this case, the number average molecular weight is more preferably 8,000 to 18,000, and still more preferably 10,000 to 14,000.
The dispersion degree of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. When the composition for forming an organic film of the present invention contains a compound containing a metal element, a mode in which the dispersion degree of the molecular weight is 1.5 or more is also preferable, and in this case, it is more preferably 1.7 or more, and still more preferably 1.8 or more. The upper limit of the dispersion degree of the molecular weight of the polyimide precursor is not particularly limited, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.8 or less, further preferably 3.2 or less, further preferably 3.1 or less, further preferably 3.0 or less, and particularly preferably 2.95 or less.
In the present specification, the degree of dispersion of molecular weights refers to a value calculated from weight average molecular weight/number average molecular weight.
[ polyimide ]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developer mainly composed of an organic solvent.
In the present specification, the alkali-soluble polyimide means a polyimide in which 0.1g or more is dissolved at 23 ℃ in 100g of a 2.38 mass% aqueous tetramethylammonium solution, and from the viewpoint of pattern formability, 0.5g or more is preferably dissolved, and 1.0g or more is more preferably dissolved. The upper limit of the amount of the above-mentioned solvent is not particularly limited, but is preferably 100g or less.
In addition, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain thereof, from the viewpoint of the film strength and the insulating property of the obtained organic film.
In the present specification, "main chain" refers to a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" refers to other bonding chains.
Fluorine atom-
The polyimide preferably has a fluorine atom from the viewpoint of the film strength of the obtained organic film.
Fluorine atom is preferably contained in R in a repeating unit represented by formula (4) described later132Or R in a repeating unit represented by the formula (4) described later131Among these, R contained as a fluorinated alkyl group in a repeating unit represented by the formula (4) described later is more preferable132Or R in a repeating unit represented by the formula (4) described later131In (1).
The amount of fluorine atoms is preferably 1 to 50mol/g, more preferably 5 to 30mol/g, based on the total mass of the polyimide.
Silicon atom-
The polyimide preferably has a silicon atom from the viewpoint of the film strength of the obtained organic film.
The silicon atom is preferably R contained in a repeating unit represented by the formula (4) described later131Among these, the organic modified (poly) siloxane structure described later is more preferably contained in the repeat represented by formula (4) described later as the organic modified (poly) siloxane structure described laterR in the unit131In (1).
Also, the above silicon atom or the above organically modified (poly) siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.
The amount of silicon atoms is preferably 0.01 to 5mol/g, more preferably 0.05 to 1mol/g, based on the total mass of the polyimide.
-ethylenic unsaturation
The polyimide preferably has an ethylenically unsaturated bond from the viewpoint of the film strength of the obtained organic film.
The polyimide may have an ethylenically unsaturated bond at the terminal of the main chain or an ethylenically unsaturated bond in the side chain, but preferably has an ethylenically unsaturated bond in the side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably R contained in a repeating unit represented by the formula (4) described later132Or R in a repeating unit represented by the formula (4) described later131Among these, R contained as a group having an ethylenically unsaturated bond in a repeating unit represented by the formula (4) described later is more preferable132Or R in a repeating unit represented by the formula (4) described later131In (1).
Among these, the ethylenically unsaturated bond is preferably R contained in a repeating unit represented by the formula (4) described later131Among these, R contained as a group having an ethylenically unsaturated bond in a repeating unit represented by the formula (4) described later is more preferable131In (1).
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having a vinyl group which is directly bonded to an aromatic ring such as a vinylphenyl group and which may be substituted, (meth) acrylamide group, (meth) acryloyloxy group, a group represented by the following formula (IV), and the like.
[ chemical formula 14]
Figure BDA0003538521080000231
In the formula (IV), R20Represents a hydrogen atom or a methyl group, preferably a methyl group.
In the formula (IV), R21Represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C (═ O) O-, -O (C ═ O) NH-, a (poly) alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3, and the number of repetitions is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or a combination of 2 or more thereof.
In these, R21A group represented by any one of the following formulae (R1) to (R3) is preferable, and a group represented by formula (R1) is more preferable.
[ chemical formula 15]
Figure BDA0003538521080000232
In the formulas (R1) - (R3), L represents a single bond, an alkylene group having 2-12 carbon atoms, a (poly) alkyleneoxy group having 2-30 carbon atoms, or a group formed by bonding 2 or more of these groups, X represents an oxygen atom or a sulfur atom, represents a bonding site with another structure, ● represents a bonding site with R in the formula (III)201The bonding site of the bonded oxygen atom.
In the formulae (R1) to (R3), a preferable embodiment of the C2-12 alkylene group or C2-30 (poly) alkyleneoxy group in L is the same as that of the above-mentioned R21In the above step (A), the preferable mode of the alkylene group having 2 to 12 carbon atoms or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the same.
In the formula (R1), X is preferably an oxygen atom.
In the formulae (R1) to (R3), the meanings are the same as those in the formula (IV), and preferred embodiments are also the same.
The structure represented by the formula (R1) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate or the like).
The structure represented by the formula (R3) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).
In formula (IV), a represents a bonding site to another structure, preferably a bonding site to a main chain of polyimide.
The amount of the ethylenically unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, based on the total mass of the polyimide.
Crosslinkable groups other than ethylenically unsaturated bonds
The polyimide may have a crosslinkable group other than an ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group or an oxetane group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably R contained in the repeating unit represented by the formula (4) described later131In (1).
The amount of the crosslinkable group other than the ethylenically unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, based on the total mass of the polyimide.
Acid value-
When the polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more, from the viewpoint of improving the developability.
The acid value is preferably 500mgKOH/g or less, more preferably 400mgKOH/g or less, and still more preferably 200mgKOH/g or less.
When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35mgKOH/g, more preferably 3 to 30mgKOH/g, and still more preferably 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, according to JIS K0070: 1992.
The acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably an acid group having a pKa of 3 to 8, from the viewpoint of both storage stability and developability.
The pKa is a negative common logarithm pKa in consideration of a dissociation reaction in which hydrogen ions are released from an acid, and the equilibrium constant Ka is expressed. In the present specification, pKa is calculated based on ACD/ChemSketch (registered trademark) unless otherwise specified. Alternatively, reference may be made to values published in "revision 5 th edition, handbook of chemistry, basic edition" edited by the Japan society.
When the acid group is a polybasic acid such as phosphoric acid, the pKa is a first dissociation constant.
The polyimide preferably contains at least 1 selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group as such an acid group.
Phenolic hydroxyl-
The polyimide preferably has a phenolic hydroxyl group from the viewpoint of optimizing the development rate with an alkaline developer.
The polyimide may have a phenolic hydroxyl group at the end of the main chain or may have a phenolic hydroxyl group in the side chain.
The phenolic hydroxyl group is preferably R contained in a repeating unit represented by formula (4) described later132Or R in a repeating unit represented by the formula (4) described later131In (1).
The amount of the phenolic hydroxyl group is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, based on the total mass of the polyimide.
The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but is preferably a compound containing a repeating unit represented by the following formula (4), more preferably a compound containing a repeating unit represented by the formula (4) and having a polymerizable group.
Formula (4)
[ chemical formula 16]
Figure BDA0003538521080000251
In the formula (4), R131Represents an organic radical having a valence of 2, R132Represents a 4-valent organic group.
When having a polymerizable group, the polymerizable group may be located at R131And R132At least one of the above-mentioned groups may be located at the terminal of the polyimide, as shown by the following formula (4-1) or formula (4-2).
Formula (4-1)
[ chemical formula 17]
Figure BDA0003538521080000252
In the formula (4-1), R133The other groups are the same as those of the formula (4) as the polymerizable group.
Formula (4-2)
[ chemical formula 18]
Figure BDA0003538521080000261
R134And R135At least one of them is a polymerizable group, and if not a polymerizable group, it is an organic group, and the other groups have the same meaning as in the formula (4).
The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group of the polyimide precursor and the like.
R131Represents an organic group having a valence of 2. Examples of the 2-valent organic group include R in the formula (2)111The same organic group is used, and the preferable range is also the same.
And as R131Examples thereof include diamine residues remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, cyclic aliphatic, and aromatic diamines. MakingSpecific examples thereof include R in the formula (2) of the polyimide precursor111Examples of (3).
From the viewpoint of more effectively suppressing the occurrence of warpage during calcination, R131Diamine residues having at least 2 alkylene glycol units in the main chain are preferred. More preferably, the diamine residue contains 2 or more ethylene glycol chains or propylene glycol chains in total or both of them in one molecule, and still more preferably a diamine residue containing no aromatic ring.
The diamine containing 2 or more ethylene glycol chains or propylene glycol chains in total in one molecule includes JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name: above, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, etc., but is not limited thereto.
R132Represents a 4-valent organic group. Examples of the organic group having a valence of 4 include R in the formula (2)115The same organic group is used, and the preferable range is also the same.
For example, as R115The 4 bonding bonds of the illustrated organic group having a valence of 4 are bonded to the 4-C (═ O) -moieties in the formula (4) to form a condensed ring.
[ chemical formula 19]
Figure BDA0003538521080000271
And, with respect to R132Examples thereof include tetracarboxylic acid residues remaining after removing the anhydride group from the tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor115Examples of (3). From the viewpoint of strength of the organic film, R132Preferably an aromatic diamine residue having 1 to 4 aromatic rings.
Also preferably in R131And R132At least one of them has an OH group. More specifically, as R131Examples thereof include 2, 2-bis (3-hydroxy-4-amino)Phenylphenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above-mentioned (DA-1) to (DA-18) are preferable examples, and R is R132More preferable examples include the above-mentioned (DAA-1) to (DAA-5).
Further, the polyimide also preferably has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
In addition, in order to improve adhesion to a substrate, an aliphatic group having a siloxane structure may be copolymerized in the polyimide. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
In order to improve the storage stability of the composition, the polyimide is preferably sealed at the end of the main chain with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a mono-active ester compound. Of these, the monoamine is more preferably used, and preferable examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, and the like, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. These may be used in 2 or more kinds, or a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.
Imidization rate (ring-closure rate) -
The imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more, from the viewpoint of film strength, insulation properties, and the like of the obtained organic film.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization ratio is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide was measured, and 1377cm, which is an absorption peak derived from the imide structure, was obtained-1Near peak intensity P1. Then, the polyimide was heat-treated at 350 ℃ for 1 hour, and the infrared absorption spectrum was measured again to determine 1377cm-1Near peak intensity P2. The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.
Imidization ratio (%) - (peak intensity P1/peak intensity P2) × 100
The polyimide may comprise a polyimide containing R of 1 species each131Or R132The repeating structural unit of the formula (4) may contain 2 or more different kinds of R131Or R132The repeating unit of the above formula (4). The polyimide may contain other kinds of repeating structural units in addition to the repeating unit of the formula (4).
The polyimide can be synthesized, for example, by a method of obtaining a polyimide precursor and completely imidizing the polyimide precursor by a known imidization method, a method of stopping the imidization reaction in the middle of the reaction and introducing a partial imide structure, and a method of introducing a partial imide structure by mixing a completely imidized polymer and the polyimide precursor, in which a tetracarboxylic dianhydride and a diamine compound (a part of which is substituted by a blocking agent which is a monoamine) are reacted at a low temperature; a method of reacting a tetracarboxylic dianhydride (a portion of which is substituted with a capping agent which is an acid anhydride or a monoacid chloride compound or a mono-active ester compound) with a diamine compound at low temperature; a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then reacting with a diamine (a portion of which is substituted with an end-capping agent as a monoamine) in the presence of a condensing agent; a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then subjecting the remaining dicarboxylic acid to acid chlorination to react with a diamine (a part of which is substituted with a capping agent as a monoamine).
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide5218 (manufactured by HUNTSMAN Corporation).
The polyimide preferably has a weight average molecular weight (Mw) of 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When 2 or more kinds of polyimides are contained, the weight average molecular weight of at least 1 kind of polyimide is preferably within the above range.
[ polybenzoxazole precursor ]
The polybenzoxazole precursor used in the present invention is not particularly limited in structure and the like, but preferably contains a repeating unit represented by the following formula (3).
Formula (3)
[ chemical formula 20]
Figure BDA0003538521080000291
In the formula (3), R121Represents an organic radical having a valence of 2, R122Represents an organic group having a valence of 4, R123And R124Each independently represents a hydrogen atom or a 1-valent organic group.
In the formula (3), R123And R124Are respectively reacted with R in the formula (2)113The meaning is the same, and the preferred range is the same. That is, at least one of them is preferably a polymerizable group.
In the formula (3), R121Represents an organic group having a valence of 2. The organic group having a valence of 2 preferably contains at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferable. R121Dicarboxylic acid residues are preferred. Only 1 kind of dicarboxylic acid residue may be used, or 2 or more kinds may be used.
The dicarboxylic acid residue is preferably a dicarboxylic acid residue containing an aliphatic group or a dicarboxylic acid residue containing an aromatic group, and more preferably a dicarboxylic acid residue containing an aromatic group.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a dicarboxylic acid composed of a linear or branched (preferably linear) aliphatic group and 2 — COOH is more preferable. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid having a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,6, 6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorsebacic acid, 1, 9-azelaic acid, Dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, tridecanedioic acid, hentriacontanedioic acid, diglycolic acid, dicarboxylic acids represented by the following formulae, and the like.
[ chemical formula 21]
Figure BDA0003538521080000301
(wherein Z is a C1-6 hydrocarbon group and n is an integer of 1-6.)
As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferable, and a dicarboxylic acid composed of only the following aromatic group and 2 — COOH groups is more preferable.
[ chemical formula 22]
Figure BDA0003538521080000302
Wherein A represents a group selected from-CH2-、-O-、-S-、-SO2-、-CO-、-NHCO-、-C(CF3)2-and-C (CH)3)2-2-valent radical in (a).
Specific examples of the aromatic group-containing dicarboxylic acid include 4,4 '-carbonyldibenzoic acid, 4' -dicarboxydiphenyl ether, and terephthalic acid.
In the formula (3), R122Represents a 4-valent organic group. As the 4-valent organic group, with R in the above formula (2)115The meaning is the same, and the preferred range is the same.
R122Also preferred are groups derived from bisaminophenol derivatives, and examples of the groups derived from bisaminophenol derivatives include 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, 3 '-diamino-4, 4' -dihydroxydiphenylsulfone, 4 '-diamino-3, 3' -dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2-bis- (4-amino-3-hydroxyphenyl) propane, 4 '-diamino-3, 3' -dihydroxybenzophenone, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxydiphenyl ether, 3 '-diamino-4, 4' -dihydroxydiphenyl ether, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, 1, 3-diamino-4, 6-dihydroxybenzene, and the like. These bisaminophenols may be used alone or in combination.
Among the bisaminophenol derivatives, those having the following aromatic group are preferable.
[ chemical formula 23]
Figure BDA0003538521080000311
In the formula, X1represents-O-, -S-, -C (CF)3)2-、-CH2-、-SO2-、-NHCO-。
[ chemical formula 24]
Figure BDA0003538521080000312
In the formula (A-s), R1Is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). R2The hydrogen atom, alkyl group, alkoxy group, acyloxy group, and cyclic alkyl group may be the same or different. R3The hydrogen atom, the linear or branched alkyl group, the alkoxy group, the acyloxy group, and the cyclic alkyl group may be the same or different.
[ chemical formula 25]
Figure BDA0003538521080000321
(in the formula (A-sc), represents the bond with the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the formula (A-s).)
In the above formula (A-s), R is considered to be in the ortho position to the phenolic hydroxyl group3The substituent also makes the carbonyl carbon of the amide bond closer to the hydroxyl group, and is particularly preferable from the viewpoint of further improving the effect of increasing the cyclization ratio at the time of curing at low temperature.
And, in the above formula (A-s), R2Is alkyl, and R3Being an alkyl group, this enables to maintain high transparency with respect to i-rays and at low temperaturesThe effect of high cyclization ratio at the time of curing is preferable.
And, in the above formula (A-s), R1Further preferred is an alkylene group or a substituted alkylene group. As R1Specific examples of the alkylene group and the substituted alkylene group of (1) include-CH2-、-CH(CH3)-、-C(CH3)2-、-CH(CH2CH3)-、-C(CH3)(CH2CH3)-、-C(CH2CH3)(CH2CH3)-、-CH(CH2CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-CH(CH(CH3)2)-、-C(CH3)(CH(CH3)2)-、-CH(CH2CH2CH2CH3)-、-C(CH3)(CH2CH2CH2CH3)-、-CH(CH2CH(CH3)2)-、-C(CH3)(CH2CH(CH3)2)-、-CH(CH2CH2CH2CH2CH3)-、-C(CH3)(CH2CH2CH2CH2CH3)-、-CH(CH2CH2CH2CH2CH2CH3)-、-C(CH3)(CH2CH2CH2CH2CH2CH3) And among them, from the viewpoint of being able to obtain a polybenzoxazole precursor having sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization ratio at the time of curing at low temperature, and being excellent in balance, more preferably-CH2-、-CH(CH3)-、-C(CH3)2-。
As a method for producing the bisaminophenol derivative represented by the formula (A-s), for example, paragraphs 0085 to 0094 and examples 1 (paragraphs 0189 to 0190) of Japanese patent laid-open publication No. 2013-256506 can be referred to, and these contents are incorporated herein.
Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese patent application laid-open No. 2013-256506, which are incorporated herein by reference. Needless to say, the present invention is not limited to these examples.
The polybenzoxazole precursor may contain other kinds of repeating structural units in addition to the repeating unit of the above formula (3).
From the viewpoint of being able to suppress the occurrence of warpage associated with ring closure, it is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit.
[ chemical formula 26]
Figure BDA0003538521080000331
In the formula (SL), Z has a structure a and a structure b, R1sIs a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms, R2sIs a hydrocarbon group of 1 to 10 carbon atoms, R3s、R4s、R5s、R6sAt least 1 of them is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and may be the same or different. The polymerization of the a structure and the b structure may be a block polymerization or a random polymerization. In the mol% of the Z portion, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.
In the formula (SL), preferable Z is R in the structure of b5sAnd R6sIs phenyl. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. When the molecular weight is within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure is more effectively reduced, and the effect of suppressing warpage and the effect of improving the solubility of the solvent can be achieved at the same time.
When the diamine residue represented by the formula (SL) is contained as another kind of repeating structural unit, it is also preferable to further contain a tetracarboxylic acid residue remaining after removing an anhydride group from a tetracarboxylic dianhydride as a repeating structural unit. Examples of such tetracarboxylic acid residues include R in the formula (2)115Examples of (3).
For example, when used in a composition described later, the polybenzoxazole precursor preferably has a weight average molecular weight (Mw) of 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the dispersion degree of the molecular weight of the polybenzoxazole precursor is not particularly limited, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.
[ polybenzoxazole ]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) and having a polymerizable group.
[ chemical formula 27]
Figure BDA0003538521080000341
In the formula (X), R133Represents an organic radical having a valence of 2, R134Represents a 4-valent organic group.
When having a polymerizable group, the polymerizable group may be located at R133And R134At least one of them may be located at the terminal of the polybenzoxazole as represented by the following formula (X-1) or formula (X-2).
Formula (X-1)
[ chemical formula 28]
Figure BDA0003538521080000342
In the formula (X-1), R135And R136At least one of them is a polymerizable group, and in the case where it is not a polymerizable group, it isOrganic group, and the other groups have the same meanings as in the formula (X).
Formula (X-2)
[ chemical formula 29]
Figure BDA0003538521080000343
In the formula (X-2), R137The other groups are substituents, and the other groups have the same meaning as in the formula (X).
The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group of the polyimide precursor and the like.
R133Represents an organic group having a valence of 2. Examples of the organic group having a valence of 2 include aliphatic or aromatic groups. Specific examples thereof include R in formula (3) of the polybenzoxazole precursor121Examples of (3). Preferred examples thereof are the same as those of R121The same is true.
R134Represents a 4-valent organic group. Examples of the organic group having a valence of 4 include R in the formula (3) of the polybenzoxazole precursor122Examples of (3). Preferred examples thereof are the same as those of R122The same is true.
For example, as R122Further, 4 bonds of the exemplified 4-valent organic group are bonded to the nitrogen atom and the oxygen atom in the formula (X) to form a condensed ring. For example, at R134In the case of the following organic group, the following structure is formed.
[ chemical formula 30]
Figure BDA0003538521080000351
The oxazole conversion of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. When the ratio of the oxazole conversion is 85% or more, the film shrinkage due to the closed ring generated by the oxazole conversion by heating becomes small, and the occurrence of warpage can be more effectively suppressed.
The polybenzoxazole can comprise R's each of 1131Or R132The repeating structural unit of the formula (X) may contain 2 or moreDifferent kinds of R in (1)131Or R132The repeating unit of the above formula (X). The polybenzoxazole may contain other kinds of repeating structural units in addition to the repeating unit of the formula (X).
Polybenzoxazole can be prepared, for example, by reacting a bisaminophenol derivative with a compound selected from the group consisting of R133The above-mentioned dicarboxylic acid or a compound of the above-mentioned dicarboxylic acid, dicarboxylic acid dichloride, dicarboxylic acid derivative, or the like is reacted to obtain a polybenzoxazole precursor, and the polybenzoxazole precursor is oxazolated by a known oxazolation reaction method.
In the case of dicarboxylic acids, an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1, 2, 3-benzotriazole or the like may be used in order to improve the reaction yield or the like.
The polybenzoxazole has a weight average molecular weight (Mw) of preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When 2 or more polybenzoxazoles are contained, the weight average molecular weight of at least 1 polybenzoxazole is preferably within the above range.
[ method for producing polyimide precursor or the like ]
The polyimide precursor and the like can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the halogenated polyester resin is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the resulting product with a diamine.
In the method for producing a polyimide precursor or the like, an organic solvent is preferably used when the reaction is carried out. The number of the organic solvents may be 1 or 2 or more.
The organic solvent can be appropriately determined depending on the raw material, but examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.
The polyimide may be produced by synthesizing a polyimide precursor and then cyclizing the precursor by a method such as thermal imidization or chemical imidization (for example, a cyclization reaction is promoted by allowing a catalyst to act), or may be directly synthesized.
Blocking agents
In the production method of a polyimide precursor or the like, in order to further improve storage stability, it is preferable to seal the ends of the polyimide precursor or the like with a sealing agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a mono-active ester compound or the like. As the blocking agent, a monoamine is more preferably used, and preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, and the like, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. These may be used in 2 or more kinds, or a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.
Solid precipitation-
The production of the polyimide precursor or the like may include a step of precipitating a solid. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor or the like is soluble, whereby a solid can be precipitated.
Then, the polyimide precursor or the like is dried to obtain a powdery polyimide precursor or the like.
[ content ]
The content of the resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and further preferably 50% by mass or more, relative to the total solid content of the composition. The content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, still more preferably 97% by mass or less, and still more preferably 95% by mass or less, based on the total solid content of the composition.
The composition of the present invention may contain only 1 kind of resin, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.
< other resins >
The composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as "other resin").
Examples of the other resin include polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, polyamideimide, a polyamideimide precursor, a phenol resin, polyamide, an epoxy resin, polysiloxane, a resin having a siloxane structure, an acrylic resin, and the like, which are different from the specific resin.
For example, by further adding an acrylic resin, a composition excellent in coatability can be obtained, and an organic film excellent in solvent resistance can be obtained.
For example, by adding an acrylic resin having a high polymerizable group value with a weight average molecular weight of 20,000 or less to the composition instead of or in addition to the polymerizable compound described later, the coatability of the composition, the solvent resistance of the organic film, and the like can be improved.
When the composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, based on the total solid content of the composition.
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass or less, based on the total solid content of the composition.
In addition, as a preferred embodiment of the composition of the present invention, a mode in which the content of other resin is low can be also adopted. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less, relative to the total solid content of the composition. The lower limit of the content is not particularly limited, and may be 0 mass% or more.
The composition of the present invention may contain only 1 kind of other resin, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.
< photosensitizers >
The compositions of the present invention preferably comprise a photosensitizer.
As the photosensitizer, a photopolymerization initiator is preferable.
[ photopolymerization initiator ]
The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.
The photopolymerization initiator is preferably a photo radical polymerization initiator. The photo radical polymerization initiator is not particularly limited, and can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. The sensitizer may be an active agent that produces a certain action with a photosensitizing agent excited by light and generates an active radical.
In the organic film, the composition of the present invention preferably contains a metal element-containing compound described later as a photo radical polymerization initiator, from the viewpoint of easily satisfying at least 1 formula selected from the above-described formulae (1) and (2). That is, in the present invention, among the metal element-containing compounds described later, a compound having a radical polymerization initiating ability can be used as a photo radical polymerization initiator.
Herein, having a radical polymerization initiating ability means that a radical capable of initiating radical polymerization can be generated. For example, when a composition containing a radical polymerizable monomer, a binder polymer, and a metal element-containing compound is irradiated with light in a wavelength region in which the metal element-containing compound absorbs light and the radical polymerizable monomer does not absorb light, the presence or absence of polymerization initiating ability can be confirmed by confirming the absence or absence of the radical polymerizable monomer. In order to confirm whether or not the monomer disappears, an appropriate method can be selected depending on the type of the radical polymerizable monomer and the binder polymer, but confirmation by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography) may be used, for example.
In the case where the composition of the present invention contains a metal element-containing compound having a radical polymerization initiating ability, etc., the composition of the present invention preferably contains substantially no radical polymerization initiator other than the metal element-containing compound. The term "substantially free of a radical polymerization initiator other than the metal element-containing compound" means that the content of a radical polymerization initiator other than the metal element-containing compound in the composition of the present invention is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass, based on the total mass of the metal element-containing compound.
Further, when the composition of the present invention contains a metal element-containing compound having a radical polymerization initiating ability, etc., the composition of the present invention also preferably contains the above metal element-containing compound and another photo radical polymerization initiator.
In the composition of the present invention, when the metal element-containing compound and the other photo radical polymerization initiator are contained, the content of the metal element-containing compound is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass, based on the total content of the metal element-containing compound and the other photo radical polymerization initiator.
The other photo radical polymerization initiator is preferably an oxime compound described later.
The photo radical polymerization initiator preferably contains at least 1 type having at least about 50L-mol in the range of about 300 to 800nm (preferably 330 to 500nm)-1·cm-1A compound having a molar absorptivity of (a).
The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer (spectrophotometer) manufactured by Varian corporation) using an ethyl acetate solvent at a concentration of 0.01 g/L.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, a compound having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference can be made to the descriptions of paragraphs 0165 to 0182 of Japanese patent laid-open publication No. 2016-027357 and paragraphs 0138 to 0151 of International publication No. 2015/199219, and the contents are incorporated in the present specification.
Examples of the ketone compound include those described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, and the contents thereof are incorporated in the present specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku co., ltd.) can also be preferably used.
In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photo radical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese patent No. 4225898 can be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184(IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: both manufactured by BASF corporation) can be used.
As the aminoacetophenone initiator, commercially available IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade names: both manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, a compound described in Japanese patent laid-open publication No. 2009-191179, which has a maximum absorption wavelength matching a light source having a wavelength of 365nm, 405nm or the like, can also be used.
Examples of the acylphosphine oxide initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide. Also, commercially available IRGACURE 819 and IRGACURE TPO (trade names: manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE 784 and IRGACURE 784EG (both manufactured by BASF corporation). The metallocene compound includes a compound containing a metal element, which is described later, and has a radical polymerization initiating ability.
As the photo radical polymerization initiator, an oxime compound is more preferably used. By using the oxime compound, the exposure latitude can be more effectively improved. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.
Specific examples of the oxime compound include compounds described in Japanese patent application laid-open Nos. 2001-233842, 2000-080068, and 2006-342166.
Preferred examples of the oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the composition of the present invention, an oxime compound (oxime-based photopolymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > C — N — O — C (═ O) -in the molecule.
[ chemical formula 31]
Figure BDA0003538521080000411
Among commercially available products, IRGACURE OXE01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (described above, manufactured by BASF CORPORATION), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photo radical polymerization initiator 2 described in Japanese patent laid-open publication No. 2012 and 014052) can also be preferably used. Also, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Also, DFI-091 (manufactured by DAITO cheimix co., ltd.) can be used.
Further, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese patent application laid-open No. 2010-262028, the compound 24 described in section 0345 of Japanese patent application laid-open No. 2014-500852, the compounds 36 to 40, and the compound (C-3) described in section 0101 of Japanese patent application laid-open No. 2013-164471.
As the most preferable oxime compound, an oxime compound having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and an oxime compound having a thioaryl group as shown in Japanese patent laid-open No. 2009-191061 are mentioned.
From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from trihalomethyl triazine (trihalomethyl triazine) compounds, benzyl dimethyl ketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl-substituted coumarin compounds.
The photo radical polymerization initiator is preferably at least 1 compound selected from the group consisting of a trihalomethyl triazine compound, an α -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound and an acetophenone compound, more preferably at least 1 compound selected from the group consisting of a trihalomethyl triazine compound, an α -aminoketone compound, an oxime compound, a triarylimidazole dimer and a benzophenone compound, still more preferably a metallocene compound or an oxime compound is used, and still more preferably an oxime compound is used.
Further, as the photo radical polymerization initiator, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone such as benzophenone, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, etc., quinones condensed with an aromatic ring such as alkylanthraquinone, benzoin compounds such as benzoin alkyl ether, benzoin compounds such as benzoin, alkyl benzoin, etc., benzyl derivatives such as benzyl dimethyl ketal, etc., can be used. Further, a compound represented by the following formula (I) can also be used.
[ chemical formula 32]
Figure BDA0003538521080000421
In the formula (I), RI00Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms, and a phenyl group or biphenyl group substituted with an alkyl group having at least 1 to 4 carbon atoms, RI01Is a group represented by the formula (II) or with RI00Same radicals, RI02～RI04Each independently being a carbon atomAn alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a halogen.
[ chemical formula 33]
Figure BDA0003538521080000422
In the formula, RI05～RI07With R of the above formula (I)I02～RI04The same is true.
Further, as the photo radical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International publication No. 2015/125469 can be used.
When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, even more preferably 1.0 to 10% by mass, based on the total solid content of the composition of the present invention. The photopolymerization initiator may contain only 1 kind, or may contain 2 or more kinds. When 2 or more kinds of photopolymerization initiators are contained, the total amount is preferably within the above range.
[ photoacid generators ]
Also, the composition of the present invention preferably contains a photoacid generator as a photosensitizer.
By containing a photoacid generator, for example, an acid is generated in an exposed portion of the composition layer, and the solubility of the exposed portion in a developer (for example, an alkaline aqueous solution) is increased, whereby a positive relief pattern in which the exposed portion is removed by the developer can be obtained.
Further, the following method can be adopted: the composition contains a photoacid generator and a polymerizable compound other than a radical polymerizable compound described later, and thus, for example, the acid generated in the exposed portion accelerates the crosslinking reaction of the polymerizable compound, whereby the exposed portion is more difficult to be removed by the developer than the unexposed portion. According to this way, a negative-type relief pattern can be obtained.
The photoacid generator is not particularly limited as long as it generates an acid by exposure, but examples thereof include onium salt compounds such as quinone diazide, diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, and sulfonate compounds such as imide sulfonate, oxime sulfonate, diazo disulfone, and o-nitrobenzyl sulfonate.
Examples of the quinone diazide compound include a quinone diazide compound in which a sulfonic acid of a quinone diazide compound is bonded to a polyhydric hydroxyl compound via an ester bond, a quinone diazide compound in which a sulfonic acid of a quinone diazide compound is bonded to a polyamino compound via a sulfonamide, and a quinone diazide compound in which a sulfonic acid of a quinone diazide compound is bonded to a polyhydric polyamino compound via at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferable that 50 mol% or more of the total functional groups of the polyol compound and the polyamino compound are substituted with quinone diazide.
In the present invention, any of 5-naphthoquinonediazide sulfonyl group and 4-naphthoquinonediazide sulfonyl group can be preferably used as the quinonediazide. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonyl ester compound extended to the g-ray region of the mercury lamp, which was suitable for g-ray exposure. In the present invention, it is preferable to select the 4-naphthoquinone diazide sulfonyl ester compound and the 5-naphthoquinone diazide sulfonyl ester compound according to the wavelength of exposure. Further, the naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or the 4-naphthoquinone diazide sulfonyl ester compound and the 5-naphthoquinone diazide sulfonyl ester compound may be contained.
The naphthoquinone diazide compound can be synthesized by an esterification reaction of a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazides, the resolution, sensitivity, and residual film ratio are further improved.
Examples of the naphthoquinone diazide include 1, 2-naphthoquinone-2-diazide-5-sulfonic acid, 1, 2-naphthoquinone-2-diazide-4-sulfonic acid, and salts and ester compounds of these compounds.
Examples of the onium salt compound or sulfonate compound include compounds described in paragraphs 0064 to 0122 of Japanese patent application laid-open No. 2008-013646.
In addition, commercially available photoacid generators can be used. Examples of commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638 and WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation).
When the photoacid generator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 2 to 15% by mass, based on the total solid content of the composition of the present invention. The photoacid generator may contain only 1 species, or may contain 2 or more species. When 2 or more kinds of photoacid generators are contained, the total amount thereof is preferably within the above range.
< Compound containing Metal element >
The composition of the present invention preferably further comprises a compound containing a metal element.
The metal element-containing compound in the present invention is preferably the photo radical polymerization initiator, from the viewpoint of further improving solvent resistance.
The compound containing a metal element is preferably an organic substance containing a metal element. That is, an organometallic compound is preferable.
Further, as the metal element in the metal element-containing compound in the present invention, iron, palladium, nickel, a group 4 element, and the like can be mentioned, but a group 4 element is preferable.
That is, the compound containing a metal element is preferably a compound containing a group 4 element, and more preferably an organic compound containing a group 4 element.
The group 4 element-containing compound is preferably an organic compound containing at least 1 atom selected from a titanium atom, a zirconium atom, and a hafnium atom, more preferably an organic compound containing at least 1 atom selected from a titanium atom and a zirconium atom, and still more preferably an organic compound containing a titanium atom. The organic compound containing at least 1 atom selected from a titanium atom and a zirconium atom is preferably an organic compound containing an organic group and a titanium atom or a zirconium atom, and the number of titanium atoms and zirconium atoms contained in one molecule of the organic compound is preferably 1 in total. The organic group is not particularly limited, but is preferably a group composed of a hydrocarbon group or a combination of a hydrocarbon group and a hetero atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom.
In the present invention, at least 1 organic group is preferably a cyclic group, and more preferably at least 2 are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably from a 5-membered cyclic group. As the cyclic group of the 5-membered ring, a cyclopentadienyl group is preferred. The organic titanium compound used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.
The compound containing a group 4 element in the present invention is preferably a compound represented by the following formula (P).
[ chemical formula 34]
Figure BDA0003538521080000451
In the formula (P), M is a group 4 element, and R independently represents a substituent.
Each R is independently preferably selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.
The group 4 element represented by M is preferably a titanium atom, a zirconium atom, and a hafnium atom, and more preferably a titanium atom and a zirconium atom.
The aromatic group in R includes an aromatic group having 6 to 20 carbon atoms, preferably an aromatic group having 6 to 20 carbon atoms, and includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
The alkyl group in R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group.
Examples of the halogen atom in R include F, Cl, Br and I.
The alkyl chain constituting the alkylsulfonyloxy group in R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl chain, an ethyl chain, a propyl chain, an octyl chain, an isopropyl chain, a tert-butyl chain, an isopentyl chain, a 2-ethylhexyl chain, a 2-methylhexyl chain, and a cyclopentyl chain.
The above R may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, and the like.
The group 4 element-containing compound used in the present invention preferably contains at least 1 selected from metallocenes and metallocene derivatives.
In the present invention, the metallocene derivative means an organometallic compound having 2 cyclopentadienyl anion derivatives having a substituent as η 5-ligand, and includes titanocene derivatives, zirconocene derivatives, hafnocene derivatives and the like.
The group 4 element-containing compound used in the present invention is preferably selected from a titanocene compound, a tetraalkoxytitanium compound, a titanium acylate compound, a titanium chelate compound, a zirconocene compound, and a hafnocene compound, more preferably from a titanocene compound, a zirconocene compound, and even more preferably from a titanocene compound and a zirconocene compound.
The group 4 element-containing compound is preferably at least 1 selected from titanocene, titanocene derivatives, zirconocene, and zirconocene derivatives, and more preferably at least 1 selected from titanocene and titanocene derivatives.
The molecular weight of the compound containing the group 4 element is preferably 50 to 2,000, more preferably 100 to 1,000.
Specific examples of the group 4 element-containing compound include tetraisopropoxytitanium, tetrakis (2-ethylhexyloxy) titanium, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonato) titanium, and the following compounds.
[ chemical formula 35]
Figure BDA0003538521080000461
Further, as the organic compound containing a titanium atom in the group 4 element-containing compound, it is also possible to use bis-cyclopentadienyl-titanium dichloride, bis-cyclopentadienyl-bisphenyltitanium, bis-cyclopentadienyl-titanium-bis-2, 3,4,5, 6-pentafluorophenyl-1-yl, bis-cyclopentadienyl-titanium-bis-2, 3,5, 6-tetrafluorophenyl-1-yl, bis-cyclopentadienyl-titanium-bis-2, 4, 6-trifluorophenyl-1-yl, bis-cyclopentadienyl-titanium-2, 6-difluorophenyl-1-yl, bis-cyclopentadienyl-titanium-bis-2, 4-difluorophenyl-1-yl, di-fluoro-1-yl, di-phenyl-1-yl, di-fluoro-1-yl, di-fluoro-phenyl-1-yl, di-fluoro-phenyl-1-yl, di-fluoro-yl, or di-phenyl-yl, Di-methylcyclopentadienyl-titanium-bis-2, 3,4,5, 6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-titanium-bis-2, 3,5, 6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-titanium-bis-2, 4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2, 6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (methylsulfonamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butylpivaloyl) -amino) phenyl ] titanium, di-methylcyclopentadienyl-titanium, di-tert-Butyl-3- (N-methyl-1-fluoro-1-yl) phenyl ] titanium, di-N-ethylcyclopentadienyl-titanium, di-2, 6-difluoro-3- (N-Butyl-1-fluoro-1-yl) phenyl ] titanium, di-methylcyclopentadienyl-titanium, di-2, 6-difluoro-3- (N-methyl-1-fluoro-phenyl) titanium, di-1-fluoro-1-titanium, di-cyclopentadienyl-fluoro-3- (2, 6-fluoro-phenyl) titanium, di-fluoro-1-titanium, di-fluoro-3-1-titanium, bis (2, 6-fluoro-bis (2, 6-fluoro-bis (2, 6-fluoro-bis (2, bis (2-bis (2, 6-bis-fluoro-bis (2, 6-bis-fluoro-bis (2, 6-bis (2, 6-fluoro-bis (2, 6) phenyl) titanium, bis (2, 6-fluoro-bis (2, 6) titanium, bis (2, bis, 6-bis, bis (2, bis, 6-bis, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethylacetoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-methylacetylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethylpropionylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethyl- (2, 2-dimethylbutyryl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (2, 2-dimethylbutyryl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-pentyl- (2, 2-dimethylbutyryl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl) - (2, 2-dimethylbutyryl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-methylbutyrylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-methylpentylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethylisobutyramido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethylacetamido) phenyl ] titanium,
Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2,2,5, 5-tetramethyl-1, 2, 5-azadichloro-1-yl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (octylsulfonamide) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (4-toluenesulfonamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (4-dodecylphenylsulfonylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (4- (1-pentylheptyl) phenylsulfonylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (ethylsulfonylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- ((4-bromophenyl) -sulfonylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2-naphthalenesulfonylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (hexadecylsulfonylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-methyl- (4-dodecylphenyl) sulfonylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-methyl-4- (1-pentylheptyl) phenyl) sulfonylamido) ] titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl- (4-tolyl) -sulfonylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (pyrrolidin-2, 5-dione-1-yl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3, 4-dimethyl-3-pyrrolidine-2, 5-dione-1-yl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (phthalimido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (isobutoxycarbonylamino) phenyl ] titanium, and a metal salt thereof, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (ethoxycarbonylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- ((2-chloroethoxy) -carbonylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (phenoxycarbonylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3-phenylthioureido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3-butylthioureido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3-phenylureido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3-butylureido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N, N-diacetamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3, 3-dimethylureido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (acetylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (butyrylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (decylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (octadecylamino) phenyl ] titanium,
Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (isobutyrylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2-ethylhexanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2-methylbutyrylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (trimethylacetamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2, 2-dimethylbutyrylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2-ethyl-2-methylheptoylamino) phenyl ] titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (cyclohexylcarbonylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2, 2-dimethyl-3-chloropropylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3-phenylpropionylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2-chloromethyl-2-methyl-3-chloropropylamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3, 4-d-formylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (4-ethylbenzoylamido) phenyl ] titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2,4, 6-trimethylphenylcarbonylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-phenylpropyl) benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-ethylheptyl) -2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isobutyl- (4-toluoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isobutylbenzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylmethyltrimethylacetamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (oxypent-2-ylmethyl) benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-ethylheptyl) -2, 2-dimethylbutyrylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-phenylpropyl- (4-toluoyl) amino) phenyl ] titanium, and titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (oxypent-2-ylmethyl) - (4-toluoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (4-toluoylmethyl) benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (4-toluoylmethyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butylbenzoylamino) phenyl ] titanium, and titanium, and titanium, and titanium, and titanium, and titanium,
Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (4-toluoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl- (4-toluoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2, 4-dimethylpentyl) -2, 2-dimethylbutyrylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2, 4-dimethylpentyl) -2, 2-dimethylpentylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- ((4-toluoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (4-toluoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) titanium, bis (2, 6-difluoro-3- ((4-toluoyl) amino) phenyl) titanium, bis (2, 2-dimethylbutyrylamino) phenyl) titanium, bis (2, bis (cyclopentadienyl) titanium, bis (2, 6-difluoro-3- ((4-dimethylpentyl) phenyl) titanium, bis (2, 2-dimethylbutyrylamino) titanium, bis (2, 6-bis (cyclopentadienyl) titanium, 6-bis (2, 6-bis (2-p-di-p-or-p-or-tert-or-tert-butyl) titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2, 2-dimethyl-3-ethoxypropionylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2, 2-dimethyl-3-allyloxypropionylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-allylacetylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2-ethylbutyrylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylmethylbenzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylmethylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethylbutyrylamino) phenyl ] titanium, bis (cyclopentadienyl) titanium, bis (2, 6-N-ethylbutyrylamino) phenyl ] titanium, bis (2, 6-difluoro-3- (N-cyclohexylmethylaminobenzoylamino) phenyl) titanium, bis (cyclopentadienyl) titanium, bis (2, 6-methyl-propionyloxy) phenyl) titanium, bis (2, 6-methyl-p-chloro-phenyl) titanium, bis (cyclopentadienyl) titanium, bis (2, 6-chloro-3-chloro-2-chloro-3-2-N-hydroxy-propionylamino) phenyl) titanium, 6-hydroxy-N-hydroxy-phenyl) titanium, bis (2, 6-hydroxy-phenyl) titanium, bis (2, bis (2, 6-hydroxy-2, or a, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylmethyl- (4-toluoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2-ethylhexyl) benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isopropylbenzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-phenylpropyl) -2, 2-dimethylpentanoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexylbenzoylamino) phenyl ] titanium, and titanium, and titanium, and titanium, and titanium, and titanium, and titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylmethyl-2, 2-dimethylpentanoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butylbenzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2-ethylhexyl) -2, 2-dimethylpentanoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl-2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isopropyl-2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-phenylpropyl) trimethylacetamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl-2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2-methoxyethyl) benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-benzylbenzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-benzyl- (4-toluoyl) amino) phenyl ] titanium, titanium oxide, and a metal oxide,
Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2-methoxyethyl) - (4-toluyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (4-methylphenylmethyl) -2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2-methoxyethyl) -2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylmethyl- (2-ethyl-2-methylheptanoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl- (2-ethyl-2-methylbutyryl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexyl-2, 2-dimethylpentanoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (oxypentan-2-ylmethyl) -2, 2-dimethylpentanoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexyl- (4-chlorobenzoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) titanium, bis (2, 6-difluoro-3- (N-cyclohexyl-2-methyl-pentanoyl) amino) phenyl) titanium, bis (2, 6-difluoro-chloro-phenyl) titanium, bis (2, bis (cyclopentadienyl) titanium, bis (2, 6-fluoro-chloro-fluoro-phenyl) titanium, bis (2-fluoro-chloro-phenyl) titanium, bis (2, 6-fluoro-chloro-fluoro-phenyl) titanium, bis (2-phenyl) titanium, bis (2, 6-chloro-fluoro-phenyl) titanium, bis (2, 6-chloro-phenyl) titanium, bis (2, 6) titanium, bis (2, bis (2, 2) titanium, or (2) or (2, 2) titanium, or (2) or (2, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexyl- (2-chlorobenzoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3, 3-dimethyl-2-azetidinon-1-yl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3-isocyanatophenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl ] titanium, and titanium, and titanium, and titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (4-tolylsulfonyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isobutyl- (4-tolylsulfonyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (2, 2-dimethyl-3-chloropropionyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-phenylpropionyl) -2, 2-dimethyl-3-chloropropionyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylmethyl- (2, 2-dimethyl-3-chloropropionyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isobutyl- (2, 2-dimethyl-3-chloropropionyl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (2-chloromethyl-2-methyl-3-chloropropionyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (butylthiocarbonylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (phenylthiocarbonylamino) phenyl ] titanium, titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3-isocyanatophenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (4-tolylsulfonyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isobutyl- (4-tolylsulfonyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (2, 2-dimethyl-3-chloropropionyl) amino) phenyl) titanium,
Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-phenylpropionyl) -2, 2-dimethyl-3-chloropropionyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylmethyl- (2, 2-dimethyl-3-chloropropionyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isobutyl- (2, 2-dimethyl-3-chloropropionyl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (2-chloromethyl-2-methyl-3-chloropropionyl) amino) phenyl ] titanium, titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (butylthiocarbonylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (phenylthiocarbonylamino) phenyl ] titanium, bis (methylcyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl-2, 2-dimethylbutyryl) amino) phenyl ] titanium, bis (methylcyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl-2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (methylcyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethylacetamido) phenyl ] titanium, bis (methylcyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethylpropionylamino) phenyl ] titanium, Bis (trimethylsilylpentadienyl) bis [ 2, 6-difluoro-3- (N-butyl-2, 2-dimethylpropionylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2-methoxyethyl) -trimethylsilylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butylhexyldimethylsilylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-ethyl- (1,1,2, -trimethylpropyl) dimethylsilylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3-ethoxymethyl-3-methyl-2-azetidinone-1-yl ] titanium ) Phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3-allyloxymethyl-3-methyl-2-azetidinon-1-yl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (3-chloromethyl-3-methyl-2-azetidinon-1-yl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-benzyl-2, 2-dimethylpropionylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (5, 5-dimethyl-2-pyrrolidone-1-yl) phenyl ] titanium, and titanium, and titanium, and titanium, and titanium, and titanium, and, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (6, 6-diphenyl-2-piperidone-1-yl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2, 3-dihydro-1, 2-benzothiazol-3-one (1, 1-dioxide) -2-yl) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl- (4-chlorobenzoyl) amino) phenyl ] titanium, and titanium, and titanium, and titanium, and titanium, and titanium,
Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-hexyl- (2-chlorobenzoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-isopropyl- (4-chlorobenzoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (4-methylphenylmethyl) - (2-chlorobenzoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl ] titanium Titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-benzyl-2, 2-dimethylpentanoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (2-ethylhexyl) -4-tolyl-sulfonyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3, 6-dioxadecyl) benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (trifluoromethylsulfonyl) amino) phenyl ] titanium, titanium, Bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (trifluoroacetylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (2-chlorobenzoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (4-chlorobenzoyl) amino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3, 6-dioxadecyl) -2, 2-dimethylpentanamido) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N- (3, 7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl ] titanium, bis (cyclopentadienyl) bis [ 2, 6-difluoro-3- (N-cyclohexylbenzoylamino) phenyl ] titanium, and the like.
Further, as the organic compound containing a zirconium atom or the compound containing a hafnium atom in the compound containing the group 4 element, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (cyclopentadienyl) methyldichloro-zirconium, (methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trimethylzirconium, (trimethylcyclopentadienyl) trimethylzirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trimethylzirconium, zirconium, hafnium, and the like, (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (pentamethylcyclopentadienyl) dimethyl (methoxy) zirconium, (cyclopentadienyl) triethylzirconium, (cyclopentadienyl) tripropylzirconium, (cyclopentadienyl) trineopentylzirconium, (cyclopentadienyl) tris (benzhydryl) zirconium, (cyclopentadienyl) dimethylzirconium hydride, (cyclopentadienyl) triethoxy zirconium, (cyclopentadienyl) triisopropoxy zirconium, (cyclopentadienyl) triphenoxy zirconium, (cyclopentadienyl) dimethylisopropoxyzirconium, (cyclopentadienyl) diphenylisopropoxyzirconium, (cyclopentadienyl) dimethoxychlorozirconium, (cyclopentadienyl) methoxydichlorozirconium, pentanediethylcyclopentadienyl) triphenylzirconium, pentakis (pentakis) trimethylzirconium, pentakis (pentamethylcyclopentadienyl) tribenzylzirconium, pentakis (pentamethylcyclopentadienyl) trichlorozirconium, pentakis (pentakis) trimethylzirconium, pentakis (pentakis) zirconium (pentakis) tripropadienyl) tripropylzirconium (cyclopentadienyl) tripropylzirconium (pentakis) trin (cyclopentadienyl) trineopentylzirconium (pentakis (cyclopentadienyl) trineopentylzirconium (trin (cyclopentadienyl) trineopentylzirconium (cyclopentadienyl) trin (cyclopentadienyl) tris (cyclopentadienyl) zirconium (cyclopentadienyl) tris (trin (cyclopentadienyl) zirconium (tris (cyclopentadienyl) zirconium (i) zirconium (i) zirconium (i) zirconium) chloride), (cyclopentadienyl) diphenoxychlorozirconium, (cyclopentadienyl) phenoxydichlorozirconium, (cyclopentadienyl) tris (phenyldimethylsilyl) zirconium, (n-butylcyclopentadienyl) dimethyl n-butoxyzirconium, (benzylcyclopentadienyl) di-m-tolylmethylzirconium, (trifluoromethylcyclopentadienyl) tribenzylzirconium, (diphenylcyclopentadienyl) dineoxymethylzirconium, (tetraethylcyclopentadienyl) tribenzylzirconium, (pentatrimethylsilylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trineopentylzirconium, (pentamethylcyclopentadienyl) methyldichlorzirconium, (pentamethylcyclopentadienyl) triethoxyzirconium, (pentamethylcyclopentadienyl) triphenoxyzirconium, (pentamethylcyclopentadienyl) methoxydichlorozirconium, (pentamethylcyclopentadienyl) diphenoxychlorozirconium, (pentamethylcyclopentadienyl) phenoxydichlorozirconium, and (pentamethylcyclopentadienyl) phenoxydichlorozirconium, (indenyl) trimethylzirconium, (indenyl) tribenzylzirconium, (indenyl) trichlorozirconium, (indenyl) trimethoxyzirconium,
(indenyl) zirconium triethoxide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium dimethoxy, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl) zirconium chlorohydroxide, bis (methylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dibenzyl, bis (methylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dibenzyl, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium chloromethyl, bis (pentamethylcyclopentadienyl) zirconium hydride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dimethyl, Bis (cyclopentadienyl) dineopentylzirconium, bis (cyclopentadienyl) di-m-tolylzirconium, bis (cyclopentadienyl) di-p-tolylzirconium, bis (cyclopentadienyl) bis (benzhydryl) zirconium, bis (cyclopentadienyl) dibromozirconium, bis (cyclopentadienyl) methylchlorozirconium, bis (cyclopentadienyl) ethylchlorozirconium, bis (cyclopentadienyl) cyclohexylchlorozirconium, bis (cyclopentadienyl) phenylchlorozirconium, bis (cyclopentadienyl) benzylchlorozirconium, bis (cyclopentadienyl) hydrogenmethylzirconium, bis (cyclopentadienyl) methoxychlorozirconium,
Bis (cyclopentadienyl) ethoxyzirconiumdichloride, bis (cyclopentadienyl) (trimethylsilyl) methylzirconium, bis (cyclopentadienyl) bis (trimethylsilyl) zirconium, bis (cyclopentadienyl) (triphenylsilyl) methylzirconium, bis (cyclopentadienyl) (tris (dimethylsilyl) methylsilicon) methylzirconium, bis (cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis (methylcyclopentadienyl) diphenylzirconium, bis (ethylcyclopentadienyl) dimethylzirconium, bis (ethylcyclopentadienyl) dichlorozirconium, bis (propylcyclopentadienyl) dimethylzirconium, bis (propylcyclopentadienyl) dichlorozirconium, bis (n-butylcyclopentadienyl) dichlorozirconium, bis (tert-butylcyclopentadienyl) bis (trimethylsilyl) zirconium, bis (hexylcyclopentadienyl) dichlorozirconium, bis (cyclohexylcyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (methylcyclopentadienyl) zirconium, bis (cyclopentadienyl) diphenylzirconium, bis (ethylcyclopentadienyl) dimethylzirconium, bis (ethylcyclopentadienyl) zirconium, bis (cyclohexylcyclopentadienyl) dimethylzirconium, bis (butylcyclopentadienyl) zirconium, bis (butylcyclopentadienyl) dimethylzirconium, bis (butylzirconium, and (butylcyclopentadienyl) zirconium, bis (butylzirconium, and (butylzirconium) bis (butylcyclopentadienyl) zirconium, and (butylzirconium) zirconium, and (butylzirconium) and (butylcyclopentadienyl) zirconium, and (butylzirconium) salts thereof, Bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (ethylmethylcyclopentadienyl) zirconium dichloride, bis (propylmethylcyclopentadienyl) zirconium dichloride, bis (butylmethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (cyclohexylmethylcyclopentadienyl) zirconium dibenzyl, bis (trimethylsilylcyclopentadienyl) zirconium dimethyl, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (trimethylgermylcyclopentadienyl) zirconium dimethyl, bis (trimethylgermylcyclopentadienyl) zirconium diphenyl, bis (trimethylstannylcyclopentadienyl) zirconium dimethyl, bis (trimethylstannylcyclopentadienyl) zirconium dibenzyl, bis (trifluoromethylcyclopentadienyl) zirconium dimethyl, Bis (trifluoromethylcyclopentadienyl) bisnorbornylzirconium, bis (indenyl) dibenzylzirconium, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, (propylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, (cyclohexylmethylcyclopentadienyl) (cyclopentadienyl) zirconium dibenzyl, (pentamethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, (trifluoromethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl, Isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, [ phenyl (methyl) methylene ] (9-fluorenyl) (cyclopentadienyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl, ethylene (9-fluorenyl) (cyclopentadienyl) zirconium dimethyl, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) zirconium dimethyl, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) zirconium dimethyl, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) zirconium dimethyl, dimethylsilylidene bis (2,3, 5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, methylenebis (cyclopentadienyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium bis (trimethylsilyl),
Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dimethyl, methylene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, ethylene bis (cyclopentadienyl) zirconium dibenzyl, ethylene bis (cyclopentadienyl) zirconium dihydride, ethylene bis (indenyl) zirconium diphenyl, ethylene bis (indenyl) zirconium methyl chloride, ethylene bis (tetrahydroindenyl) zirconium dibenzyl, isopropylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, isopropylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dihydride, dimethylsilylene bis (cyclopentadienyl) dineopentylzirconium, dimethylsilylene bis (cyclopentadienyl) zirconium dihydride, dimethylsilylene bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride, Dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) (fluorenyl) zirconium dihydride, dimethylsilylenebis (methylcyclopentadienyl) (fluorenyl) zirconium dihydride, dimethylsilylenebis (3-trimethylsilylcyclopentadienyl) zirconium dihydride, dimethylsilylenebis (indenyl) zirconium dimethyl, diphenylsilylbis (indenyl) zirconium dichloride, phenylmethylsilylbis (indenyl) zirconium dichloride, and compounds obtained by substituting a hafnium atom for a zirconium atom of these compounds.
In addition, examples of the compound containing a metal element include compounds containing an iron atom, a palladium atom, a nickel atom, and the like.
The compound containing an iron atom is preferably a complex containing an iron atom, and more preferably a metallocene compound such as ferrocene.
As the compound containing a palladium atom or a nickel atom, a complex containing a palladium atom or a nickel atom is more preferable.
The compound containing an iron atom, a palladium atom, a nickel atom, or the like may or may not have a radical polymerization initiating ability, but preferably has a radical polymerization initiating ability.
The content of the compound containing a metal element is preferably 0.1 to 30% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.
The metal element-containing compound may be used in 1 kind or 2 or more kinds. In the case of using 2 or more species, the total amount is preferably within the above range.
In the composition of the present invention, the mass ratio of the content of the metal element-containing compound to the content of the onium salt or other thermal alkali generator described later is preferably a ratio of the metal element-containing compound: the ratio of the onium salt or other thermal alkali-producing agent is 99:1 to 1:99, more preferably 90:10 to 10:90, and still more preferably 40:60 to 20: 80. By setting within such a range, a higher ring-closure rate and a higher glass transition temperature of the precursor at a low temperature can be achieved.
< polymerizable Compound >
[ radical polymerizable Compound ]
The composition of the present invention preferably contains a polymerizable compound.
As the polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group. The radical polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyloxy group from the viewpoint of reactivity.
The number of radical polymerizable groups of the radical polymerizable compound may be 1 or 2 or more, but the radical polymerizable compound preferably has 2 or more radical polymerizable groups, and more preferably 3 or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.
The molecular weight of the radical polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, further preferably 900 or less, and particularly preferably 600 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.
From the viewpoint of developability, the composition of the present invention preferably contains at least 12 or more functional radically polymerizable compounds containing 2 or more radically polymerizable groups, and more preferably contains at least 13 or more functional radically polymerizable compounds. Further, a mixture of a 2-functional radical polymerizable compound and a 3-or more-functional radical polymerizable compound may be used. For example, the number of functional groups of the 2 or more functional polymerizable monomer means that the number of radical polymerizable groups in one molecule is 2 or more.
Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, and preferably esters of an unsaturated carboxylic acid and a polyol compound, and amides of an unsaturated carboxylic acid and a polyamine compound. Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group (sulfide group) with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, and the like can also be preferably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having dissociative substituent groups such as halogeno group and tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols are preferable. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, a vinyl ether, an allyl ether, or the like may be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent laid-open No. 2016-027357, which are incorporated herein by reference.
The radical polymerizable compound is also preferably a compound having a boiling point of 100 ℃ or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane and then (meth) acrylating, urethane (meth) acrylates as described in Japanese patent publication Sho-48-041708, Japanese patent publication Sho-50-006034, Japanese patent laid-open Sho-51-037193, and the like, Polyester acrylates described in Japanese Kokai publication Sho-48-064183, Japanese Kokoku publication Sho-49-043191 and Japanese Kokoku publication Sho-52-030490, polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, methyl acrylate, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also preferable. Further, there can be also mentioned a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid.
Further, as preferable radical polymerizable compounds other than the above, compounds having 2 or more groups having a fluorene ring and an ethylenically unsaturated bond, described in japanese patent application laid-open nos. 2010-160418, 2010-129825, 4364216, and the like, and cardo resins can be used.
Further, as other examples, specific unsaturated compounds described in Japanese patent publication No. 46-043946, Japanese patent publication No. 01-040337, and Japanese patent publication No. 01-040336, vinylphosphonic acid-based compounds described in Japanese patent publication No. 02-025493, and the like can be cited. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, compounds described as photopolymerizable monomers and oligomers in Japan Society of attachment (Journal of the Society of Japan) vol.20, No.7, pages 300 to 308 (1984) can also be used.
In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219 can be preferably used, and these contents are incorporated in the present specification.
Further, as the radical polymerizable compound, a compound obtained by adding ethylene oxide and propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resultant, which is described as formula (1) and formula (2) in jp-a-10-062986, and a specific example thereof, can also be used.
Further, as other radical polymerizable compounds, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can be used, and the contents thereof are incorporated in the present specification.
As the radical polymerizable compound, dipentaerythritol triacrylate (as a commercially available product, KAYARAD-330; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD-320; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD-310; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd., manufactured by A-DPH; Shin-Nakamura Chemical Co., manufactured by Ltd.), and a structure in which (meth) acryloyl groups thereof are bonded via ethylene glycol residues or propylene glycol residues are preferable. Oligomeric forms of these can also be used.
Commercially available products of the radical polymerizable compound include SR-494 which is a 4-functional acrylate having 4 vinyloxy chains manufactured by Sartomer Company, Inc, SR-209, 231, 239 which is a 2-functional acrylate having 4 vinyloxy chains manufactured by Sartomer Company, Inc, TPA-60 which is a 6-functional acrylate having 6 pentenyloxy chains manufactured by Ltd, TPA-330 which is a 3-functional acrylate having 3 isobutenoxy chains, urethane oligomer UAS-10, UAB-140(NIPPON PAPER INSTRIES CO., LTD., manufactured by LTD., NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200(Shin-Nakamura Co., Ltd., manufactured by Ltd.), DPHA-40H (Nippon Kayak Co., manufactured by Chemical Co., Ltd.), and TPA-9300 which are manufactured by Chemical Co., Ltd.), and SR-209, 231, 239, Nippon Kayak-60 which are manufactured by Ltd, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLENMER PME400 (manufactured by NOF corporation), etc.
As the radical polymerizable compound, urethane acrylates having an ethylene oxide skeleton as described in Japanese patent publication No. 48-041708, Japanese patent publication No. 51-037193, Japanese patent publication No. 02-032293 and Japanese patent publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton as 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 preferable. As the radical polymerizable compound, compounds having an amino structure or a thioether structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238 can be used.
The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. The radical polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydric compound and an unsaturated carboxylic acid, and more preferably a radical polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydric compound. In particular, the aliphatic polyhydroxy compound is preferably a compound in which pentaerythritol or dipentaerythritol is used as the aliphatic polyhydroxy compound in the radical polymerizable compound having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. Examples of commercially available products include M-510 and M-520 which are polybasic acid-modified acrylic acid oligomers produced by TOAGOSEI CO., LTD.
The preferable acid value of the radical polymerizable compound having an acid group is 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. When the acid value of the radical polymerizable compound is within the above range, the production workability is excellent, and the developability is excellent. Further, the polymerizability is good. The acid value is measured in accordance with JIS K0070: 1992.
The composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound from the viewpoint of suppressing warpage accompanied by control of the elastic modulus of the organic film. As the monofunctional radical polymerizable compound, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylate amide, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate. The monofunctional radical polymerizable compound is preferably a compound having a boiling point of 100 ℃ or higher under normal pressure in order to suppress volatilization before exposure.
[ polymerizable Compound other than the above-mentioned radical polymerizable Compound ]
The composition of the present invention may further contain a polymerizable compound other than the above-mentioned radical polymerizable compound. Examples of the polymerizable compound other than the radical polymerizable compound include compounds having a methylol group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine compound.
Compounds having hydroxymethyl, alkoxymethyl or acyloxymethyl groups
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.
[ chemical formula 36]
Figure BDA0003538521080000601
(wherein t represents an integer of 1 to 20, R104A t-valent organic group having 1 to 200 carbon atoms, R105Is represented by-OR106or-OCO-R107A group represented by R106R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms107Represents an organic group having 1 to 10 carbon atoms. )
[ chemical formula 37]
Figure BDA0003538521080000602
(in the formula, R404A 2-valent organic group having 1 to 200 carbon atoms, R405Is represented by-OR406or-OCO-R407A group represented by R406R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms407Represents an organic group having 1 to 10 carbon atoms. )
[ chemical formula 38]
Figure BDA0003538521080000603
(wherein u represents an integer of 3 to 8, R504A u-valent organic group having 1 to 200 carbon atoms, R505Is represented by-OR506or-OCO-R507A group represented by R506R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms507Represents an organic group having 1 to 10 carbon atoms. )
Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (hereinafter, trade name: ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name: Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name: Sanwa Chemical co., LTD), 2,6-dimethoxymethyl-4-t-butylphenol (2, 6-dimethylymethyl-4-t-butyl-cresol), 2,6-dimethoxymethyl-p-cresol (2, 6-dimethylymethyl-4-t-cresol), 2, 6-dimethylacyloxy-2-cresol (2, 6-dimethylcresol, 6-diacetoxymethyl-p-cresol), and the like.
Specific examples of the compound represented by the formulｃA (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASI YUKIZAI CORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by SanwｃA Chemical co., LTD.).
Epoxy compound (compound having epoxy group) -
As the epoxy compound, a compound having 2 or more epoxy groups in one molecule is preferable. The epoxy group undergoes a crosslinking reaction at 200 ℃ or lower, and a dehydration reaction resulting from crosslinking does not occur, so that film shrinkage is less likely to occur. Therefore, the epoxy compound is effective for low-temperature curing and warpage suppression of the composition.
The epoxy compound preferably contains a polyethylene oxide group. This can further reduce the elastic modulus and suppress warpage. The polyethylene oxide group is a group having a repeating unit number of ethylene oxide of 2 or more, and the repeating unit number is preferably 2 to 15.
Examples of the epoxy compound include bisphenol a type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, but the epoxy group-containing silicones are not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (above, which is a product name, DIC manufacture), EPICLON RIKARESIN (registered trademark) BEO-60E (registered trademark), NEICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (registered trademark), EPICLON Corporation, L4003S, EP, EP-4000, LpanO-4000, manufactured by ADEKA CORPORATION), and the like. Among them, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint of excellent warpage suppression and heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain a polyethylene oxide group, and are therefore preferable.
Oxetane compound (compound having oxetanyl group) -
Examples of the oxetane compound include a compound having 2 or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester, and the like. Specifically, ARON oxoetane series (for example, OXT-121, OXT-221, OXT-191, and OXT-223) manufactured by TOAGOSEI co.
-benzoxazine compound (compound having benzoxazolyl group) -
The benzoxazine compound is preferable because the crosslinking reaction derived from the ring-opening addition reaction does not generate outgassing at the time of curing, and further reduces thermal shrinkage to suppress the occurrence of warpage.
Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (hereinafter, trade name, manufactured by SHIKOKU CHEMICALS CORPORATION), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac type dihydrobenzoxazine compound. These may be used alone, or 2 or more kinds may be mixed.
The content of the polymerizable compound is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the 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 still more preferably 30% by mass or less.
The polymerizable compound may be used alone in 1 kind, but may be used in combination with 2 or more kinds. When 2 or more kinds are used in combination, the total amount is preferably within the above range.
< solvent >
The composition of the present invention preferably contains a solvent. The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, e-caprolactone, δ -valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.) (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl n-butylacetate, ethyl ethoxyacetate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc, Ethyl 2-oxobutyrate, and the like.
Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene.
Preferable examples of the sulfoxide include dimethyl sulfoxide.
Preferable examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.
The solvent is preferably mixed in 2 or more types from the viewpoint of improving the properties of the coated surface.
In the present invention, 1 kind of solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent comprising 2 or more kinds thereof is preferable. Particularly preferably, dimethyl sulfoxide and gamma-butyrolactone are used in combination.
From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method.
The solvent may contain only 1 species, or may contain 2 or more species. When 2 or more solvents are contained, the total amount is preferably within the above range.
< thermal polymerization initiator >
The composition of the present invention may include a thermal polymerization initiator, and particularly, may include a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates a polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, the resin and the polymerizable compound can be polymerized in the heating step described later, and therefore, the solvent resistance can be further improved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063554.
When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass, based on the total solid content of the composition of the present invention. The thermal polymerization initiator may contain only 1 species, or may contain 2 or more species. When 2 or more thermal polymerization initiators are contained, the total amount thereof is preferably within the above range.
< thermal acid generating agent >
The composition of the present invention may comprise a thermal acid generator.
The thermal acid generator generates an acid by heating, and has an effect of promoting a crosslinking reaction of at least 1 compound selected from the group consisting of a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound.
The thermal decomposition initiation temperature of the thermal acid generator is preferably 50 to 270 ℃, more preferably 50 to 250 ℃. Further, it is preferable to select, as the thermal acid generator, a substance which does not generate an acid when the composition is dried (prebaking: about 70 to 140 ℃ C.) after being coated on a substrate and generates an acid when the composition is finally heated (curing: about 100 to 400 ℃ C.) after patterning in the subsequent exposure and development, because a decrease in sensitivity during development can be suppressed.
The pyrolysis starting temperature was determined as the peak temperature of the exothermic peak at the lowest temperature when the thermal acid generator was heated to 500 ℃ at 5 ℃/min in the pressure-resistant capsule.
Examples of the apparatus used for measuring the pyrolysis initiation temperature include Q2000 (manufactured by TA Instruments Japan inc.).
The acid generated by the thermal acid generator is preferably a strong acid, and for example, aryl sulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, alkyl sulfonic acid such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, and haloalkyl sulfonic acid such as trifluoromethanesulfonic acid are preferable. An example of such a thermal acid generator is the thermal acid generator described in paragraph 0055 of jp 2013-a 072935.
Among them, from the viewpoint of reducing the residue in the organic membrane and preventing the deterioration of the physical properties of the organic membrane, a thermal acid generator which generates an alkylsulfonic acid having 1 to 4 carbon atoms or a haloalkylsulfonic acid having 1 to 4 carbon atoms, preferably, a thermal acid generator which generates an alkylsulfonic acid having 1 to 4 carbon atoms, a methanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, (4- ((methoxycarbonyl) oxy) phenyl) dimethylsulfonium) methanesulfonate, a methanesulfonic acid benzyl (4- ((methoxycarbonyl) oxy) phenyl) methylthioninium, a methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, a trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, a trifluoromethanesulfonic acid (4- ((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, a trifluoromethanesulfonic acid benzyl (4-hydroxyphenyl) methylthioninium, a trifluoromethanesulfonic acid, Benzyl (4- ((methoxycarbonyl) oxy) phenyl) methylthioninium trifluoromethanesulfonate, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium trifluoromethanesulfonate, 3- (5- (((propylsulfonyl) oxy) imino) thiophen-2 (5H) -ylidene) -2- (o-tolyl) propionitrile, and 2, 2-bis (3- (methylsulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferable as the thermal acid generator.
Further, the compound described in paragraph 0059 of Japanese patent application laid-open No. 2013-167742 is also preferable as a thermal acid generator.
The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, per 100 parts by mass of the resin. The content of 0.01 parts by mass or more can promote the crosslinking reaction, and thus the mechanical properties and solvent resistance of the organic film can be further improved. From the viewpoint of electrical insulation of the organic film, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.
< onium salt >
The compositions of the present invention preferably comprise an onium salt.
In particular, when the polyimide precursor is contained as another resin, the composition preferably contains an onium salt.
The kind of onium salt is not particularly limited, but preferable examples thereof include ammonium salts, imine salts, sulfonium salts, iodonium salts, and phosphonium salts.
Among these, ammonium salts or imide salts are preferable from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts, or phosphonium salts are preferable from the viewpoint of compatibility with the polymer.
The onium salt is a salt of a cation having an onium structure and an anion, and the cation and the anion may be bonded to each other through a covalent bond or may not be bonded to each other through a covalent bond.
That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or may be an intermolecular salt in which cation molecules and anion molecules of different molecules are ionically bonded, but is preferably an intermolecular salt. In the composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded to each other by an ionic bond or may be dissociated from each other.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least 1 kind of cation selected from a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
The onium salt used in the present invention may be a thermal alkali-generating agent.
The thermal base generator is a compound which generates a base by heating, and examples thereof include an acidic compound which generates a base when heated to 40 ℃ or higher.
[ ammonium salt ]
In the present invention, ammonium salt means a salt of an ammonium cation with an anion.
Ammonium cation-
As ammonium cation, quaternary ammonium cations are preferred.
Further, as the ammonium cation, a cation represented by the following formula (101) is preferable.
[ chemical formula 39]
Figure BDA0003538521080000661
In the formula (101), R1～R4Each independently represents a hydrogen atom or a hydrocarbon group, R1～R4At least 2 of which may be bonded to each other to form a ring.
In the formula (101), R1～R4Each independently is preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R1～R4Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like.
At R1～R4In the case where at least 2 of them are bonded to each other to form a ring, the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
The ammonium cation is preferably represented by any one of the following formulae (Y1-1) and (Y1-2).
[ chemical formula 40]
Figure BDA0003538521080000671
In the formulae (Y1-1) and (Y1-2), R101Represents an n-valent organic radical, R1And R in the formula (101)1Same meaning of, Ar101And Ar102Each independently represents an aryl group, and n represents an integer of 1 or more.
In the formula (Y1-1), R101Preferably an aliphatic hydrocarbon, an aromatic hydrocarbon or a group obtained by removing n hydrogen atoms from the bonded structure, and more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene or naphthalene.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.
In the formula (Y1-2), Ar101And Ar102Each independently is preferably phenyl or naphthyl, more preferably phenyl.
Anions-
The anion in the ammonium salt is preferably 1 selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion, and the carboxylic acid anion is more preferable from the viewpoint of compatibility between the stability and the pyrolysis property of the salt. That is, the ammonium salt is more preferably a salt of an ammonium cation with a carboxylic acid anion.
The carboxylic acid anion is preferably an anion of a 2-valent or higher carboxylic acid having 2 or more carboxyl groups, and more preferably an anion of a 2-valent carboxylic acid. According to this embodiment, the stability, curability, and developability of the composition can be further improved. In particular, the use of an anion of a 2-valent carboxylic acid can further improve the stability, curability, and developability of the composition.
The carboxylic acid anion is preferably represented by the following formula (X1).
[ chemical formula 41]
Figure BDA0003538521080000681
In the formula (X1), EWG represents an electron withdrawing group.
In the present embodiment, the electron-withdrawing group means a group having a hammett substituent constant σ m that shows a positive value. Here, σ m is described in detail in Journal of Synthetic Organic Chemistry, Japan 23, book No. 8 (1965) p.631-642, all by Hippon-Tou. The electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.
Examples of the substituent in which σ m represents a positive value include CF3Base (. sigma.m.0.43), CF3C (═ O) group (σ m ═ 0.63), HC ≡ C group (σ m ═ 0.21), CH ≡ C group2CH (σ m) group (0.06), Ac (σ m) group (0.38), MeOC (O) group (σ m) 0.37), MeC (O) CH (CH) group (σ m) 0.21), PhC (O) group (σ m) 0.34), H2NC(＝O)CH2And a group (σ m ═ 0.06). In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (the same applies hereinafter).
The EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).
[ chemical formula 42]
Figure BDA0003538521080000682
In the formulae (EWG-1) to (EWG-6),Rx1～Rx3each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.
In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA).
[ chemical formula 43]
Figure BDA0003538521080000683
In the formula (XA), L10Represents a single bond or is selected from alkylene, alkenylene, aromatic group, -NRXA 2-valent linking group in a combination of these, RXRepresents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.
Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion, and oxalic acid anion.
From the viewpoint that cyclization of the specific resin is easily performed at low temperature and storage stability of the composition is easily improved, the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt preferably contains an anion having a conjugate acid pka (pka) of 2.5 or less as an anion, and more preferably contains an anion of 1.8 or less.
The lower limit of the pKa is not particularly limited, but is preferably-3 or more, more preferably-2 or more, from the viewpoint of preventing the generated base from being easily neutralized and improving the cyclization efficiency of a specific resin or the like.
As the pKa, there can be used values described in physical identification of the organic structure (author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; editor: Braude, E.A., Nachod, F.C.; academic Press, New York, 1955), biochemical research data (author: Dawson, R.M.C., etc.; Oxford, Clalundun Press, 1959). For the compounds not described in these documents, values calculated from the structural formulae using software of ACD/pKa (manufactured by ACD/Labs) were used.
Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these.
[ chemical formula 44]
Figure BDA0003538521080000691
[ Iminium salt ]
In the present invention, an imide salt means a salt of an imide cation with an anion. Examples of the anion include the same anions as those in the ammonium salt, and preferred embodiments are also the same.
Imide cation-
As the imine cation, a pyridinium cation is preferable.
Further, as the imide cation, a cation represented by the following formula (102) is also preferable.
[ chemical formula 45]
Figure BDA0003538521080000701
In the formula (102), R5And R6Each independently represents a hydrogen atom or a hydrocarbon group, R7Represents a hydrocarbon group, R5～R7At least 2 of which may be bonded to each other to form a ring.
In the formula (102), R5And R6And R in the above formula (101)1～R4The meaning is the same, and the preferred mode is the same.
In the formula (102), R is preferred7And R5And R6At least 1 of which is bonded to form a ring. The above rings may contain heteroatoms. Examples of the hetero atom include a nitrogen atom. The ring is preferably a pyridine ring.
The imide cation is preferably represented by any one of the following formulae (Y1-3) to (Y1-5).
[ chemical formula 46]
Figure BDA0003538521080000702
In the formulae (Y1-3) to (Y1-5)，R101Represents an n-valent organic radical, R5And R in the formula (102)5Have the same meaning as R7And R in the formula (102)7The same meaning, n represents an integer of 1 or more, and m represents an integer of 0 or more.
In the formula (Y1-3), R101Preferably an aliphatic hydrocarbon, an aromatic hydrocarbon or a group obtained by removing n hydrogen atoms from the bonded structure, and more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.
In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and still more preferably 1.
Specific examples of the imide salt include the following compounds, but the present invention is not limited to these.
[ chemical formula 47]
Figure BDA0003538521080000711
[ sulfonium salt ]
In the present invention, sulfonium salt means a salt of a sulfonium cation and an anion. Examples of the anion include the same anions as those in the ammonium salt, and preferred embodiments are also the same.
Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.
The sulfonium cation is preferably a cation represented by the following formula (103).
[ chemical formula 48]
Figure BDA0003538521080000712
In the formula (103), R8～R10Each independently represents a hydrocarbon group.
R8～R10Independently of one another preferablyAn alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.
R8～R10Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like. Among these, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R8～R10The same groups may be used or different groups may be used, but from the viewpoint of synthesis suitability, the same groups are preferable.
[ iodonium salt ]
In the present invention, an iodonium salt means a salt of an iodonium cation with an anion. Examples of the anion include the same anions as those in the ammonium salt, and preferred embodiments are also the same.
Iodonium cation-
As the iodonium cation, a diaryliodonium cation is preferable.
Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
[ chemical formula 49]
Figure BDA0003538521080000721
In the formula (104), R11And R12Each independently represents a hydrocarbon group.
R11And R12Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.
R11And R12May have a substituent, and as examples of the substituent,examples thereof include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R11And R12The same groups may be used or different groups may be used, but from the viewpoint of synthesis suitability, the same groups are preferable.
[ phosphonium salt ]
In the present invention, phosphonium salts refer to salts of phosphonium cations with anions. Examples of the anion include the same anions as those in the ammonium salt, and preferred embodiments are also the same.
Phosphonium cation-
The phosphonium cation is preferably a quaternary phosphonium cation, and examples thereof include a tetraalkylphosphonium cation, a triarylmonoalkylphosphonium cation and the like.
Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
[ chemical formula 50]
Figure BDA0003538521080000731
In the formula (105), R13～R16Each independently represents a hydrogen atom or a hydrocarbon group.
R13～R16Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and yet still more preferably a phenyl group.
R13～R16Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like. Among these, the substituent is preferably an alkyl group or an alkoxy group, and more preferably a branched alkyl group or an alkyl groupThe oxy group is more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R13～R16The same groups may be used or different groups may be used, but from the viewpoint of synthesis suitability, the same groups are preferable.
When the composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, still more preferably 0.85% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less.
The onium salt may be used in 1 species or 2 or more species. In the case of using 2 or more species, the total amount is preferably within the above range.
< thermal alkali production agent >
The composition of the present invention may comprise a thermal base generator.
In particular, in the case where the composition contains a polyimide precursor as another resin, the composition preferably contains a thermal alkali generator.
The thermal alkali-producing agent may be a compound corresponding to the onium salt, or may be a thermal alkali-producing agent other than the onium salt.
Examples of the other thermal alkali-producing agent include nonionic thermal alkali-producing agents.
Examples of the nonionic thermoalcogenating agent include compounds represented by the formula (B1) or the formula (B2).
[ chemical formula 51]
Figure BDA0003538521080000741
In the formulae (B1) and (B2), Rb1、Rb2And Rb3Each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb1And Rb2Not both as hydrogen atoms. And the number of the first and second electrodes,Rb1、Rb2and Rb3None have a carboxyl group. In the present specification, the tertiary amine structure refers to a structure in which 3 bonds of a nitrogen atom having a valence of 3 are all covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, the carbon atom is not limited thereto.
In the formulae (B1), (B2), Rb1、Rb2And Rb3Preferably at least 1 of them comprises a cyclic structure, more preferably at least 2 comprise a cyclic structure. The cyclic structure may be a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring in which 2 monocyclic rings are condensed. Monocyclic rings are preferably 5-membered rings or 6-membered rings, preferably 6-membered rings. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.
More specifically, Rb1And Rb2Preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms). These groups may have a substituent in a range in which the effect of the present invention is exerted. Rb1And Rb2May be bonded to each other to form a ring. The ring to be formed is preferably a 4-to 7-membered nitrogen-containing heterocycle. Rb1And Rb2Particularly preferred is a linear, branched or cyclic alkyl group which may have a substituent (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), more preferred is a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), and further preferred is a cyclohexyl group which may have a substituent.
As Rb3Examples thereof include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, still more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, still more preferably 2 to 12 carbon atoms, further preferably 2 to 6 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, further preferably 7 to c19, more preferably 7 to 12), an aralkenyl group (preferably 8 to 24, still more preferably 8 to 20, further more preferably 8 to 16 carbon atoms), an alkoxy group (preferably 1 to 24, more preferably 2 to 18, further more preferably 3 to 12 carbon atoms), an aryloxy group (preferably 6 to 22, more preferably 6 to 18, further more preferably 6 to 12 carbon atoms), or an aralkyloxy group (preferably 7 to 23, more preferably 7 to 19, further more preferably 7 to 12 carbon atoms). Among them, preferred are cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), aralkenyl groups, and aralkyloxy groups. Rb3The compound may have a substituent in a range in which the effect of the present invention is exerted.
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
[ chemical formula 52]
Figure BDA0003538521080000751
In the formula, Rb11And Rb12And Rb31And Rb32Respectively with Rb in formula (B1)1And Rb2The same is true.
Rb13The alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms) may have a substituent within a range in which the effects of the present invention are exhibited. Wherein, Rb is13Aralkyl groups are preferred.
Rb33And Rb34Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms), and preferably a hydrogen atom.
Rb35Preferably an alkyl group (preferably 1 to 24, more preferably 1 to 12, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12, more preferably 2 to 10, further preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably 7 to 23, more preferably 7 to 19, further preferably 7 to 12 carbon atoms), and preferably an aryl group.
The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1 a).
[ chemical formula 53]
Figure BDA0003538521080000752
Rb11And Rb12And Rb in the formula (B1-1)11And Rb12The meaning is the same.
Rb15And Rb16The alkyl group is preferably a hydrogen atom, an alkyl group (preferably a carbon number of 1 to 12, more preferably 1 to 6, further preferably 1 to 3), an alkenyl group (preferably a carbon number of 2 to 12, more preferably 2 to 6, further preferably 2 to 3), an aryl group (preferably a carbon number of 6 to 22, more preferably 6 to 18, further preferably 6 to 10), an aralkyl group (preferably a carbon number of 7 to 23, more preferably 7 to 19, further preferably 7 to 11), and preferably a hydrogen atom or a methyl group.
Rb17The aromatic hydrocarbon group preferably has 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, further preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), and among them, an aryl group is preferable.
The molecular weight of the nonionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.
Specific examples of the compound as the thermal alkali-producing agent in the onium salt and other specific examples of the thermal alkali-producing agent include the following compounds.
[ chemical formula 54]
Figure BDA0003538521080000771
[ chemical formula 55]
Figure BDA0003538521080000781
[ chemical formula 56]
Figure BDA0003538521080000791
The content of the thermal alkali-producing agent is preferably 0.1 to 50% by mass based on the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. The thermal alkali generator can be used in 1 or more than 2 kinds. In the case of using 2 or more species, the total amount is preferably within the above range.
< migration inhibitor >
The compositions of the present invention also preferably comprise a migration inhibitor. By including the migration inhibitor, migration of metal ions originating from the metal layer (metal wiring) into the composition layer can be effectively inhibited.
The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-piperazine ring, 6H-piperazine ring, and triazine ring), thiourea compounds, compounds having a sulfur group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
Alternatively, an ion scavenger that scavenges anions such as halogen ions can also be used.
As other migration inhibitors, there can be used rust inhibitors described in paragraph 0094 of Japanese patent application laid-open No. 2013-015701, compounds described in paragraphs 0073-0076 of Japanese patent application laid-open No. 2009-283711, compounds described in paragraph 0052 of Japanese patent application laid-open No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese patent application laid-open No. 2012-194520, compounds described in paragraph 0166 of International publication No. 2015/199219, and the like.
Specific examples of the migration inhibitor include the following compounds.
[ chemical formula 57]
Figure BDA0003538521080000801
When the composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the composition.
The number of migration inhibitors may be only 1, or may be 2 or more. In the case where the migration inhibitor is 2 or more, the total amount is preferably within the above range.
< polymerization inhibitor >
The compositions of the invention preferably contain a polymerization inhibitor.
As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycoletherdiamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 1-t-butylphenol, p-cresol, p-t-butylhydroquinone, 1, 4-nitroso-6-m-ylbenzeneamine, p-tolylphenol, 4-aminothiophene, and the like are preferably used, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) benzene, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-tert-butyl) phenylmethane and the like. Further, the polymerization inhibitor described in paragraph 0060 of Japanese patent laid-open publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication No. 2015/125469 can also be used.
The following compound (Me is methyl) can be used.
[ chemical formula 58]
Figure BDA0003538521080000811
When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.05 to 2.5% by mass, based on the total solid content of the composition of the present invention.
The polymerization inhibitor may be only 1 type or may be 2 or more types. When the polymerization inhibitor is 2 or more, the total amount is preferably within the above range.
< modifier for improving adhesion of Metal >
The composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to a metal material used for an electrode, a wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent and the like.
Examples of the silane coupling agent include a compound described in paragraph 0167 of International publication No. 2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International publication No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and a compound described in paragraph 0055 of International publication No. 2014/097594. Further, as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358, it is also preferable to use 2 or more different silane coupling agents. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.
[ chemical formula 59]
Figure BDA0003538521080000821
Further, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 and thioether compounds described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935 can be used.
The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. When the lower limit value is not less than the lower limit value, the adhesion between the organic film and the metal layer after the curing step is good, and when the upper limit value is not more than the upper limit value, the heat resistance and the mechanical properties of the organic film after the curing step are good. The number of the metal adhesion improver may be only 1, or 2 or more. In the case of using 2 or more species, the total amount is preferably within the above range.
< other additives >
The composition of the present invention may contain, as necessary, various additives, for example, a sensitizer such as N-phenyldiethanolamine, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, and the like. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.
[ sensitizer ]
The compositions of the present invention may comprise a sensitizer. The sensitizer absorbs the specific active radiation to become an electron excited state. The sensitizer in the electron excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and functions such as electron transfer, energy transfer, and heat generation are generated. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases.
Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine.
As the sensitizer, a sensitizer dye can be used.
The details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
When the composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass, based on the total solid content of the composition of the present invention. The sensitizer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
[ chain transfer agent ]
The composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in page 683-684 of The third edition of The Polymer dictionary (Kobunshi Jiten) (The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. These groups of compounds can generate radicals by supplying hydrogen to low-activity radicals or by deprotonating after oxidation. In particular, a thiol compound can be preferably used.
Further, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International publication No. 2015/199219 can be used.
When the composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the composition of the present invention. The chain transfer agent may be only 1 kind or 2 or more kinds. In the case where the number of the chain transfer agents is 2 or more, the total amount is preferably within the above range.
[ surfactant ]
Various surfactants may be added to the composition of the present invention in order to further improve coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Also, the following surfactants are also preferable. In the following formulae, the parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain indicate the number of repetitions of each repeating unit.
[ chemical formula 60]
Figure BDA0003538521080000841
Further, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International publication No. 2015/199219 can also be used.
When the composition of the present invention contains a surfactant, 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 of the present invention. The number of the surfactants may be only 1, or may be 2 or more. When the surfactant is 2 or more, the total amount is preferably within the above range.
[ higher fatty acid derivatives ]
With respect to the composition of the present invention, in order to prevent polymerization inhibition by oxygen, higher fatty acid derivatives such as behenic acid, behenamide may be added, which is biased to the surface of the composition during drying after coating.
Further, as the higher fatty acid derivative, a compound described in paragraph 0155 of international publication No. 2015/199219 can be used.
When the composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the composition of the present invention. The number of the higher fatty acid derivatives may be only 1, or may be 2 or more. In the case where the number of the higher fatty acid derivatives is 2 or more, the total amount is preferably within the above range.
< restrictions on other contained substances >
From the viewpoint of the properties of the coated surface, the moisture content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass.
From the viewpoint of insulation properties, the metal content of the composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. In the case where a plurality of metals are contained, it is preferable that the total of these metals is within the above range.
Further, as a method for reducing metal impurities unintentionally contained in the composition of the present invention, there can be mentioned: selecting a raw material having a small metal content as a raw material constituting the composition of the present invention; filtering the raw materials constituting the composition of the present invention with a filter; a method of lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation or the like under conditions that inhibit contamination as much as possible.
In view of the use as a semiconductor material, the content of halogen atoms in the composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm, from the viewpoint of corrosion of wiring. Among these, the substance present in the state of the halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. Preferably, the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is within the above-mentioned range.
As the container for the composition of the present invention, a conventionally known container can be used. Further, as the storage container, in order to suppress the mixing of impurities into the raw material and the composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is made of 6 kinds of 6-layer resins or a bottle in which 6 kinds of resins are made into a 7-layer structure. Examples of such a container include those disclosed in Japanese patent laid-open publication No. 2015-123351.
< preparation of the composition >
The composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
In addition, in order to remove foreign matter such as dust and fine particles in the composition, filtration using a filter is preferably performed. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one previously cleaned with an organic solvent. In the filter filtration step, a plurality of filters may be connected in series or in parallel for use. When a plurality of filters are used, filters having different pore sizes or different materials may be used in combination. Also, multiple filtrations of various materials may be performed. In the case of performing filtration a plurality of times, it may be circulation filtration. Also, pressurization and filtration may be performed. In the case of pressurizing and filtering, the pressure to be pressurized is preferably 0.05MPa or more and 0.3MPa or less.
In addition to filtration using a filter, a process of removing impurities using an adsorbent may be performed. The filter filtration and the impurity removal treatment using the adsorbent material 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.
Use of organic membranes
The organic film of the present invention is preferably used for an interlayer insulating film for a rewiring layer.
In addition, the present invention can also be used for an insulating film or a stress buffer film of a semiconductor device.
(composition)
The composition of the present invention is a composition for use in the formation of the organic film of the present invention.
The components contained in the composition of the present invention have the same meanings as those of the components contained in the composition described above for the organic film, and preferred embodiments thereof are also the same.
The composition of the present invention is preferably a curable composition which is cured by exposure to light, heat, or the like.
(organic film, laminate, semiconductor device, and methods for producing these)
Next, the organic film, the laminate, the semiconductor device, and the methods for manufacturing these will be described.
The organic film of the present invention is preferably a cured product of a coating film of the composition. The thickness of the organic film of the present invention can be set to, for example, 0.5 μm or more, and can also be set to 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less.
The organic film of the present invention can be laminated into a laminate by laminating 2 or more layers and further 3 to 7 layers. The laminate of the present invention is preferably a laminate having 2 or more organic films and a metal layer between the organic films. The laminate of the present invention preferably includes 2 or more organic films and a metal layer between any of the organic films. For example, a laminate having a layer structure in which at least 3 layers of a first organic film, a metal layer, and a second organic film are sequentially stacked is preferable. The first organic film and the second organic film are both the organic film of the present invention, and for example, a preferable embodiment is one in which the first organic film and the second organic film are both films obtained by curing the composition of the present invention. The composition of the present invention used for forming the first organic film and the composition of the present invention used for forming the second organic film may be the same composition or may be different compositions, but from the viewpoint of production suitability, the compositions of the present invention are preferably the same composition. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.
Examples of the field to which the organic film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and a stress buffer film. In addition, a sealing film, a substrate material (a base film, a cover layer, an interlayer insulating film of a flexible printed circuit board), an insulating film for mounting as described above, and the like may be patterned by etching. For these applications, for example, reference can be made to Science & Technology co, ltd. "high functionalization and application Technology of polyimide" 4 months 2008, kaki benaying jogming/master edition, CMC Publishing co, ltd. "foundation and development of polyimide material" 11 months 2011 issue, japan polyimide aromatic polymer research institute/edition "latest polyimide foundation and application" NTS inc., 8 months 2010, and the like.
The organic film of the present invention can also be used for manufacturing a printing plate such as an offset printing plate or a screen printing plate, etching a molding member, manufacturing a protective varnish or a dielectric layer in electronics, particularly microelectronics, and the like.
The method for producing an organic film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") preferably includes a film-forming step of applying the composition (the composition of the present invention) to a substrate to form a film.
Further, the method for producing an organic film of the present invention preferably further includes the film forming step, and further includes an exposure step of exposing the film to light and a development step of developing the film (of performing a development treatment on the film).
Further, the method for producing an organic film of the present invention preferably further comprises the film forming step (and the developing step as needed), and further comprises a heating step of heating the film at 50 to 450 ℃.
Specifically, the method preferably includes the following steps (a) to (d).
(a) Film-forming step for forming a film (composition layer) by applying the composition to a substrate
(b) An exposure step of exposing the film after the film formation step
(c) A developing step of developing the exposed film
(d) A heating step of heating the developed film at 50 to 450 DEG C
By heating in the heating step, the composition layer after development can be further cured. In this heating step, for example, the thermal alkali generator is decomposed to obtain sufficient curability.
The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing an organic film according to the present invention. In the method for producing a laminate of the present embodiment, after the organic film is formed according to the method for producing an organic film, the step (a), the steps (a) to (c), and the steps (a) to (d) are further performed again. In particular, it is preferable to sequentially perform each of the above steps a plurality of times, for example, 2 to 5 times (i.e., 3 to 6 times in total). By thus laminating the organic films, a laminate can be produced. In the present invention, it is particularly preferable to provide a metal layer on the upper side of the portion where the organic film is provided, or between the organic films, or both. In addition, in the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, the steps (a), preferably (a) to (c) or (a) to (d) are performed a plurality of times, whereby a laminate of organic films can be obtained.
< film formation step (layer formation step) >
The production method according to a preferred embodiment of the present invention includes a film formation step (layer formation step) of applying the composition to a substrate to form a film (layer).
The type of the substrate may be appropriately determined depending On the application, and is not particularly limited, for example, a substrate made of a semiconductor such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, or amorphous silicon, a substrate made of quartz, Glass, an optical thin film, a ceramic material, a vapor-deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, paper, SOG (Spin On Glass), a TFT (thin film transistor) array substrate, or an electrode plate of a Plasma Display Panel (PDP).
In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate is more preferable.
As the substrate, for example, a plate-like substrate (substrate) can be used.
When a composition layer is formed on the surface of a resin layer such as a composition layer or the surface of a metal layer, the resin layer or the metal layer serves as a base material.
As a method for applying the composition to a substrate, coating is preferable.
Specifically, examples of the application method include a dip coating method, an air knife coating method, a curtain coating method, a bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, an ink jet method, and the like. From the viewpoint of uniformity of the thickness of the composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and in the case of a circular substrate such as a wafer, a spin coating method, a spray coating method, an ink jet method, and the like are preferable, and in the case of a rectangular substrate, a slit coating method, a spray coating method, an ink jet method, and the like are preferable. In the case of spin coating, for example, the coating can be applied at a rotation speed of 500 to 2,000rpm (revolutions per minute) for about 10 seconds to 1 minute.
Further, a method of transferring a coating film formed on the temporary support by the above application method in advance onto a substrate can also be applied.
As the transfer method, the production methods described in paragraphs 0023, 0036 to 0051 of Japanese patent application laid-open No. 2006-023696 and paragraphs 0096 to 0108 of Japanese patent application laid-open No. 2006-047592 can also be preferably used in the present invention.
< drying Process >
The production method of the present invention may include a step of drying to remove the solvent after the film (composition layer) is formed and after the film forming step (layer forming step). The preferable drying temperature is 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably 90 to 110 ℃. The drying time may be, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
< Exposure Process >
The production method of the present invention may include an exposure step of exposing the film (composition layer) to light. The exposure amount is not particularly limited as long as the composition can be cured, but is preferably 100 to 10,000mJ/cm in terms of exposure energy at a wavelength of 365nm, for example2More preferably 200 to 8,000mJ/cm2。
The exposure wavelength can be suitably determined within the range of 190 to 1,000nm, preferably 240 to 550 nm.
The exposure wavelength includes, in terms of the relationship with the light source, (1) semiconductor laser (wavelength of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength of 436nm), h-ray (wavelength of 405nm), i-ray (wavelength of 365nm), broadband (g-ray, h-ray, 3 wavelengths of i-ray), (4) excimer laser, KrF excimer laser (wavelength of 248nm), ArF excimer laser (wavelength of 193nm), F2 excimer laser (wavelength of 157nm), (5) extreme ultraviolet ray; EUV (wavelength 13.6nm), (6) electron beam, and the like. As for the composition of the present invention, in particular, exposure based on a high-pressure mercury lamp is preferable, and among them, exposure based on i-ray is preferable. Thereby, particularly high exposure sensitivity can be obtained.
< developing Process >
The production method of the present invention may include a development step of performing a development treatment on the exposed film (composition layer). By performing development, an unexposed portion (unexposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as spin-coating immersion, spraying, dipping, or ultrasonic waves can be used.
The development is performed using a developer. As the developer, the following can be used without particular limitation: a developer in which an unexposed portion (unexposed portion) of the composition layer is removed if the composition is a negative composition, or a developer in which an exposed portion (exposed portion) is removed if the composition is a positive composition.
In the present invention, the case where an alkaline developer is used as the developer is referred to as alkaline development, and the case where a developer containing 50 mass% or more of an organic solvent is used as the developer is referred to as solvent development.
In the alkaline development, the content of the organic solvent in the developer is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably no organic solvent is contained, with respect to the total mass of the developer.
The developing solution in the alkaline development is preferably an aqueous solution with a pH of 9-14.
Examples of the alkaline compound contained in the developer in the alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia, and amine. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and the like. Among them, alkali compounds containing no metal are preferable, and ammonium compounds are more preferable.
The number of the basic compounds may be only 1, or may be 2 or more. When the number of the basic compounds is 2 or more, the total amount is preferably within the above range.
In the solvent development, the developer more preferably contains 90% or more of an organic solvent. 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 the structural formula to ChemBioDraw.
As the organic solvent, preferable examples of the ester include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.; and ethers, for example, preferably include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.; and as the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable; preferable examples of the sulfoxide include dimethyl sulfoxide.
In the present invention, among others, cyclopentanone and γ -butyrolactone are preferable, and cyclopentanone is more preferable.
The developer is preferably an organic solvent in an amount of 50% by mass or more, more preferably an organic solvent in an amount of 70% by mass or more, and still more preferably an organic solvent in an amount of 90% by mass or more. Further, 100% by mass of the developer may be an organic solvent.
The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly specified, but can be generally controlled at 20 to 40 ℃.
After the treatment with the developer, further rinsing may be performed.
In the case of solvent development, the rinsing is preferably performed using an organic solvent different from the developer.
In the case of alkaline development, the rinsing is preferably performed using pure water.
The rinsing time is preferably 5 seconds to 1 minute.
< heating Process >
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ℃.
The heating step is preferably included after the film formation step (layer formation step), the drying step, and the development step.
In this step, a curing reaction of an unreacted polymerizable compound other than the specific resin, a curing reaction of an unreacted polymerizable group in the specific resin, and the like, which are contained in the composition of the present invention, can be performed.
When the specific resin is a polyimide precursor and the composition contains a thermal alkali generator, the thermal alkali generator decomposes to generate a base, for example, in the heating step, and a cyclization reaction of the polyimide precursor proceeds.
The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ℃ or higher, more preferably 80 ℃ or higher, further preferably 140 ℃ or higher, particularly preferably 150 ℃ or higher, further preferably 160 ℃ or higher, and most preferably 170 ℃ or higher. The upper limit is preferably 450 ℃ or lower, more preferably 350 ℃ or lower, still more preferably 250 ℃ or lower, and particularly preferably 220 ℃ or lower.
The heating is preferably performed at a temperature rise rate of 1 to 12 ℃/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ℃/min, and still more preferably 3 to 10 ℃/min. The temperature rise rate is set to 1 ℃/min or more, whereby excessive volatilization of the amine can be prevented while ensuring productivity, and the temperature rise rate is set to 12 ℃/min or less, whereby the residual stress of the organic film can be relaxed.
The temperature at the start of heating is preferably from 20 ℃ to 150 ℃, more preferably from 20 ℃ to 130 ℃, and still more preferably from 25 ℃ to 120 ℃. The temperature at the start of heating is the temperature at the start of the heating step to the maximum heating temperature. For example, when the composition is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably gradually increased from a temperature 30 to 200 ℃ lower than the boiling point of the solvent contained in the composition.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
In particular, in the case of forming a multilayer laminate, the heating temperature is preferably 180 to 320 ℃, more preferably 180 to 260 ℃, from the viewpoint of adhesion between the layers of the organic film. Although the reason for this is not clear, it is considered that: by setting the temperature to this temperature, the polymerizable groups in the resin between the layers are subjected to a crosslinking reaction with each other.
The heating may be performed in stages. As an example, the following pretreatment process may be performed: the temperature was raised from 25 ℃ to 180 ℃ at 3 ℃/min and maintained at 180 ℃ for 60 minutes, from 180 ℃ to 200 ℃ at 2 ℃/min and maintained at 200 ℃ for 120 minutes. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. The film characteristics can be improved by such a pretreatment process. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in 2 stages or more, and for example, the pretreatment step 1 may be carried out at a temperature of 100 to 150 ℃ and the pretreatment step 2 may be carried out at a temperature of 150 to 200 ℃.
Further, the heating and cooling may be performed, and the cooling rate at this time is preferably 1 to 5 ℃/min.
In the heating step, it is preferable to perform the heating step in an environment having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, from the viewpoint of preventing decomposition of the resin. The oxygen concentration is preferably 50ppm (by volume) or less, more preferably 20ppm (by volume) or less.
< Process for Forming Metal layer >
The production method of the present invention preferably includes a metal layer formation step of forming a metal layer on the surface of the film (composition layer) after the development treatment.
The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper.
The method for forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in Japanese patent laid-open Nos. 2007-157879, 2001-521288, 2004-214501 and 2004-101850 can be used. For example, photolithography, lift-off, electroplating, electroless plating, etching, printing, a method of combining these, and the like are considered. More specifically, a pattern forming method combining sputtering, photolithography, and etching, and a pattern forming method combining photolithography and plating are given.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, in terms of the thickest part.
< laminating Process >
The production method of the present invention preferably further comprises a lamination step.
The lamination step is a series of steps including (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step, which are sequentially performed again on the surface of the organic film (resin layer) or the metal layer. However, the film forming step (a) may be repeated. The heating step (d) may be performed at the end or in the middle of the lamination. That is, the following method may be adopted: repeating the steps (a) to (c) a predetermined number of times, and then heating the layer (d), thereby collectively curing the stacked composition layers. In addition, the developing step (c) may be followed by the metal layer forming step (e), and in this case, the heating step (d) may be performed every time, or the heating step (d) may be performed after the lamination step is performed a predetermined number of times. Needless to say, the lamination step may appropriately include the drying step, the heating step, and the like.
In the case where the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment may be exemplified.
The laminating step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.
For example, the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less, as in the case of resin layer/metal layer/resin layer/metal layer.
In the present invention, it is particularly preferable that the organic film (resin layer) of the composition is formed so as to cover the metal layer after the metal layer is provided. Specifically, the following modes are exemplified: the film forming step (a), the exposure step (b), the development step (c), the metal layer forming step (e), and the heating step (d) are sequentially repeated, or the film forming step (a), the exposure step (b), the development step (c), and the metal layer forming step (e) are sequentially repeated, and the heating step (d) is provided at the end or in the middle. By alternately performing the laminating step of laminating the composition layer (resin layer) and the metal layer forming step, the composition layer (resin layer) and the metal layer can be alternately laminated.
The invention also discloses a semiconductor device comprising the organic film or the laminate of the invention. As a specific example of a semiconductor device in which the composition of the present invention is used for forming an interlayer insulating film for a rewiring layer, reference can be made to the descriptions in paragraphs 0213 to 0218 of Japanese patent laid-open No. 2016-027357 and the description of FIG. 1, and these contents are incorporated in the present specification.
Examples
The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Hereinafter, "part" and "%" are based on mass unless otherwise specified.
(Synthesis of polyimide precursor resin PA-1)
While removing water in a dry reactor equipped with a flat bottom joint equipped with a stirrer, a condenser and an internal thermometer, oxydiphthalic dianhydride (20.0 g, 64.5 mmol) was suspended in 140mL of diglyme. 10.1g (77 mmol) of 2-hydroxyethyl methacrylate, 12.6g (39 mmol) of BLEMER AP-400 (manufactured by NOF CORPORATION), 0.05g of hydroquinone, and 10.7g (135 mmol) of pyridine were continuously added thereto, and the mixture was stirred at 60 ℃ for 18 hours. Subsequently, after the mixture was cooled to-20 ℃, 16.1g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Subsequently, the mixture was heated to room temperature (23 ℃) and stirred for 2 hours, and then 9.7g (123 mmol) of pyridine and 25mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Subsequently, to the obtained transparent solution was added dropwise a solution prepared by dissolving 11.7g (58.7 mmol) of 4, 4' -diaminodiphenyl ether as diamine in 100mL of NMP over 1 hour. During the addition of the above diamine, the viscosity increases. Subsequently, methanol 5.6g (17.5 mmol) and 3, 5-di-tert-butyl-4-hydroxytoluene 0.05g were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Subsequently, the obtained polyimide precursor resin was dried at 45 ℃ for 1 day under reduced pressure. The molecular weight of the polyimide precursor resin PA-1 was 25,100 and Mn was 13,200.
The structure of PA-1 is presumed to be represented by the following formula (PA-1). In the formula (PA-1), a bonding site of an oxygen atom bonded to R is represented.
[ chemical formula 61]
Figure BDA0003538521080000951
In the above (PA-1), in C3H6The above-mentioned formulas (A) and (B) randomly include 1-methylvinyl group (formula (P1)) and 2-methylvinyl group (formula (P2)). In the formulae (P1) and (P2)1Bonded to the acryloyloxy side structure of R in the formula (PA-1)2Bonded to the structure on the x side in R in formula (PA-1).
[ chemical formula 62]
Figure BDA0003538521080000952
< examples and comparative examples >
In each example, the components shown in table 1 below were mixed to obtain each composition. In comparative examples, the components shown in table 1 below were mixed to obtain respective compositions for comparison.
The obtained composition and comparative composition were passed through a polytetrafluoroethylene filter having a pore width of 0.8 μm and subjected to pressure filtration.
In table 1, the numerical values shown in the respective columns indicate the contents (mass%) of the respective components in the composition.
The numerical values in the column of "total" indicate the total value (mass%) of the contents of the components in the composition.
In table 1, the expression "-" indicates that the corresponding component is not contained.
[ Table 1]
Figure BDA0003538521080000961
The details of each component described in table 1 are as follows.
[ solvent ]
NMP: n-methyl pyrrolidone
GBL: gamma-butyrolactone
DMSO: dimethyl sulfoxide
EL: lactic acid ethyl ester
[ initiator ]
OXE 01: irgacure OXE01 (manufactured by BASF corporation)
784 EG: irgacure 784EG (manufactured by BASF corporation)
[ resin ]
PA-1: the polyimide precursor resin PA-1 synthesized as described above
[ polymerizable Compound ]
SR 209: SR-209 (tetraethylene glycol dimethacrylate, manufactured by Sartomer Company, Inc)
DPHA: dipentaerythritol hexaacrylate (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)
[ silane coupling agent ]
S-1 to S-2: a compound of the structure
[ chemical formula 63]
Figure BDA0003538521080000971
[ polymerization inhibitor ]
F-1: 1, 4-benzoquinones
F-2: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd., the following structure)
[ chemical formula 64]
Figure BDA0003538521080000972
[ onium salt or thermal alkali-producing agent ]
T-1: a compound of the structure
[ chemical formula 65]
Figure BDA0003538521080000973
[ migration inhibitor ]
H-1: 1H-tetrazole
H-2: a compound of the structure
[ chemical formula 66]
Figure BDA0003538521080000981
< evaluation >
[ Small Angle Neutron Scattering (SANS) measurement ]
The compositions prepared in examples and comparative examples or comparative compositions were applied to a silicon wafer by spin coating to form a resin layer.
The obtained silicon wafer having the resin layer formed thereon was dried on a hot plate at 100 ℃ for 5 minutes, thereby obtaining a composition layer of about 15 μm in uniform thickness on the silicon wafer. Using a stepper (Nikon NSR 2005i9C), at 500mJ/cm2The obtained composition layer was subjected to full-area exposure. After the exposure, the temperature was raised at a rate of 10 ℃/min under a nitrogen atmosphere to 180 ℃ and then heated for 3 hours. The cured composition layer (organic film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the organic film was peeled from the silicon wafer.
The organic film having a thickness of about 15 μm obtained by the above method was cut into a circular shape having a diameter of 18mm so that the thickness was 100 to 200 μm, and the resulting film was used as a measurement sample. After measuring the mass and film thickness of the above measurement samples, the samples were filled in a sample holder dedicated for SANS measurement of J-PARC MLF iMATERIA and sealed.
Small-angle neutron scattering measurements were performed using a sample holder filled with the above-described measurement specimens using J-PARC MLF iMATERIA (BL 20). Specifically, the sample rack was set in a 40-link automatic sample changer dedicated for SANS measurement, and automatic measurement was performed. The measurement conditions are as follows.
In order to calculate the relative intensity values, measurements were performed using empty sample holders not filled with the measurement samples under the same measurement conditions as the above measurements.
Determination of conditions
MLF neutron beam output: 500kW
Determination of q-value region:
Figure BDA0003538521080000982
(group of small angle detectors using the above J-PARC MLF iMATERIA (BL 20))
Figure BDA0003538521080000983
And low angle detector set
Figure BDA0003538521080000984
)
Measuring temperature: room temperature (23 ℃ C.)
And (3) accumulating time: 12 to 15 minutes per sample
Based on the measurement results, values of I/A and I/B were calculated in each of examples and comparative examples and are shown in the column "I/A" or "I/B" in Table 1, respectively.
[ evaluation of solvent resistance ]
The compositions prepared in examples and comparative examples or comparative compositions were applied to a silicon wafer having a diameter of 4 inches by spin coating, respectively, to form a resin layer.
The obtained silicon wafer having the resin layer formed thereon was dried on a hot plate at 100 ℃ for 5 minutes, thereby obtaining a composition layer of about 15 μm in uniform thickness on the silicon wafer. Using a stepper (Nikon NSR 2005i9C), at 500mJ/cm2The obtained composition layer was subjected to full-area exposure. After the above exposure, the temperature was raised at a rate of 10 ℃/min under a nitrogen atmosphere to 180 ℃, and then heated for 3 hours to obtain a silicon wafer having an organic film formed thereon.
After the above heating, the film thickness (film thickness a) of the organic film on the silicon wafer was measured. Then, the silicon wafer having the organic film formed thereon was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropyl alcohol, and then air-dried. After the air drying, the film thickness (film thickness B) of the organic film on the silicon wafer was measured.
The residual ratio (%) of the film thickness of the organic film was calculated from the following formula, and the calculated value is shown in the column "solvent resistance (% unit)" in table 1.
The larger the residual ratio (%) of the film thickness of the organic film, the more excellent the solvent resistance of the obtained organic film.
The residual ratio (%) of the film thickness of the organic film (film thickness B/film thickness a × 100)
[ evaluation of elongation at break ]
The compositions prepared in examples and comparative examples or comparative compositions were applied to a silicon wafer by spin coating to form a resin layer.
The obtained silicon wafer having the resin layer formed thereon was dried on a hot plate at 100 ℃ for 5 minutes, thereby obtaining a composition layer of about 15 μm in uniform thickness on the silicon wafer. Using a stepper (Nikon NSR 2005i9C), at 500mJ/cm2The obtained composition layer was subjected to full-area exposure. After the exposure, the temperature was raised at a rate of 10 ℃/min under a nitrogen atmosphere to 180 ℃ and then heated for 3 hours. The cured composition layer (organic film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the organic film was peeled from the silicon wafer.
The peeled organic film was punched with a punch to prepare a test piece having a sample width of 3mm and a sample length of 30 mm. The elongation in the longitudinal direction of the obtained test piece was measured using a tensile tester (Tensilon) in an environment of a crosshead speed of 300 mm/min, 25 ℃ and 65% RH (relative humidity) in accordance with JIS-K6251. Each measurement was performed 5 times, and the arithmetic mean of the elongation at break (elongation at break) of the test piece in the 5 measurements is shown in the column of "elongation at break (% by unit)" in table 1.
The larger the arithmetic average value, the more excellent the elongation at break of the obtained organic film.
From the above results, it is understood that the organic film of the present invention is excellent in solvent resistance.
In the comparative composition of comparative example 1, both the formula (1) and the formula (2) were not satisfied, I/a was 2.413 and I/B was 0.419. The organic film of comparative example 1 was found to have poor solvent resistance.
Next, solvent resistance and elongation at break were evaluated by the same methods as in example 1, using 3 compositions each using a closed-loop polyimide resin, a resin containing a polybenzoxazole precursor, or a closed-loop polybenzoxazole instead of the resin PA-1 of example 1. In the case of using any of the above 3 compositions, results were obtained in which the solvent resistance and the elongation at break were at the same levels as in example 1.
< example 101 >
The composition described in example 1 was spin-coated on the surface of a copper thin layer in a resin substrate having a copper thin layer formed on the surface thereof so that the film thickness became 20 μm. After the composition coated on the resin substrate was dried at 100 ℃ for 2 minutes, exposure was performed using a stepper (manufactured by Nikon Corporation, NSR1505 i 6). Through a mask of a square pattern (a square pattern of 100 μm in length and width, the number of repetitions is 10), at a wavelength of 365nm, at 400mJ/cm2The exposure was carried out at the exposure dose of (1) to produce a square residual pattern. After exposure, development was performed with cyclopentanone for 30 seconds and with PGMEA for 20 seconds, thereby obtaining a pattern.
Next, the temperature was raised at a rate of 10 ℃/min under a nitrogen atmosphere to 180 ℃, and then heated at that temperature for 3 hours, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer has excellent insulating properties. Then, it was confirmed that the semiconductor device was operated without any problem as a result of manufacturing the semiconductor device using the interlayer insulating film for the rewiring layer.

Claims (8)

1. An organic film satisfying at least 1 formula selected from the following formula (1) and the following formula (2),
formula (1): I/A is more than or equal to 2.5;
formula (2): I/B is more than or equal to 0.5;
in the formula (1) or the formula (2), I is q at
Figure FDA0003538521070000011
In the range of (a) is q, the maximum value of the relative intensity value when the neutron small angle scattering measurement is performed on the organic film
Figure FDA0003538521070000012
In the range of (a) is the minimum value of the relative intensity values when the neutron small angle scattering measurement is performed on the organic film, B is q is
Figure FDA0003538521070000013
In the range of (a) is a minimum value of relative intensity values when neutron small angle scattering measurement is performed on the organic film, Q is a value defined by the following formula (Q) in small angle scattering,
formula (Q): q ═ 4 pi/λ sin θ;
in the formula (Q), λ is the wavelength of the neutron beam, and θ is the scattering angle of the neutron beam.
2. The organic film according to claim 1, which is a cured product of a coating film of a composition containing at least 1 resin selected from the group consisting of polyimide, polybenzoxazole, a polyimide precursor, and a polybenzoxazole precursor.
3. The organic film according to claim 2,
the composition comprises a photosensitizer.
4. A composition for use in the formation of an organic film according to any one of claims 1 to 3.
5. A laminate comprising 2 or more layers of the organic film of any one of claims 1 to 3 and a metal layer between any of the organic films.
6. A semiconductor device comprising the organic film of any one of claims 1 to 3 or the laminate of claim 5.
7. A method for producing an organic film, which comprises a film-forming step of applying the composition to a substrate to form a film, wherein the organic film is produced according to any one of claims 1 to 3.
8. The method for producing an organic film according to claim 7, comprising a step of heating the film at 50 to 450 ℃.
CN202080063592.5A 2019-09-25 2020-09-04 Organic film, method for producing same, composition, laminate, and semiconductor device Pending CN114402256A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2019174186 2019-09-25
JP2019-174186 2019-09-25
PCT/JP2020/033513 WO2021059917A1 (en) 2019-09-25 2020-09-04 Organic film and manufacturing method therefor, composition, laminate, and semiconductor device

Publications (1)

Publication Number Publication Date
CN114402256A true CN114402256A (en) 2022-04-26

Family

ID=75166595

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080063592.5A Pending CN114402256A (en) 2019-09-25 2020-09-04 Organic film, method for producing same, composition, laminate, and semiconductor device

Country Status (5)

Country Link
JP (2) JP7204937B2 (en)
KR (1) KR20220041166A (en)
CN (1) CN114402256A (en)
TW (1) TW202112910A (en)
WO (1) WO2021059917A1 (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004063271A2 (en) * 2003-01-07 2004-07-29 Massachusetts Institute Of Technology Structured baroplastic materials
US20120134909A1 (en) * 2010-08-20 2012-05-31 Aerogel Technologies, Llc Porous nanostructured polyimide networks and methods of manufacture
CN107615166B (en) 2015-08-21 2020-12-25 旭化成株式会社 Photosensitive resin composition, method for producing polyimide, and semiconductor device
TWI728137B (en) * 2016-06-29 2021-05-21 日商富士軟片股份有限公司 Negative photosensitive resin composition, cured film, cured film manufacturing method, semiconductor device, laminated body manufacturing method, semiconductor device manufacturing method, and polyimide precursor
JP7450323B2 (en) * 2017-08-30 2024-03-15 住友ゴム工業株式会社 Rubber composition and its manufacturing method

Also Published As

Publication number Publication date
WO2021059917A1 (en) 2021-04-01
TW202112910A (en) 2021-04-01
JPWO2021059917A1 (en) 2021-04-01
JP7204937B2 (en) 2023-01-16
KR20220041166A (en) 2022-03-31
JP2023041680A (en) 2023-03-24

Similar Documents

Publication Publication Date Title
KR20190021423A (en) Photosensitive resin composition, cured film, laminate, method of producing cured film, method of producing laminate and semiconductor device
JP7289353B2 (en) Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and polyimide or polyimide precursor
JP7431050B2 (en) Resin composition, cured film, laminate, method for producing cured film, and semiconductor device
CN113614130A (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
KR102636334B1 (en) Pattern formation method, photosensitive resin composition, cured film, laminate, and device
JPWO2019013240A1 (en) Thermosetting resin composition, cured film thereof, laminate, semiconductor device, and methods for producing the same
TWI785264B (en) Photosensitive resin composition, cured film, laminate, method for producing cured film, semiconductor element, and thermal alkali generator
TW202045590A (en) Curable resin composition, cured film, multilayer body, method for producing cured film, and semiconductor device
TWI802640B (en) Photosensitive resin composition, resin, cured film, laminate, method for producing cured film, semiconductor element
JP7265627B2 (en) Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor
TW202116876A (en) Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, resin, and method for producing resin
CN114730132A (en) Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and resin
TW202112907A (en) Curable resin composition, cured film, layered product, method for producing cured film, semiconductor device, resin, and method for producing resin
TW202110958A (en) Curable resin composition, method for producing curable resin composition, cured film, multilayer body, method for producing cured film, and semiconductor device
JP7196121B2 (en) Pattern forming method, photosensitive resin composition, laminate manufacturing method, and electronic device manufacturing method
JP7334248B2 (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
CN115667404A (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
CN114730145A (en) Pattern forming method, photocurable resin composition, method for producing laminate, and method for producing electronic device
CN114402256A (en) Organic film, method for producing same, composition, laminate, and semiconductor device
TWI803717B (en) Photosensitive resin composition, pattern forming method, cured film, laminate and device
TWI837236B (en) Pattern forming method, photosensitive resin composition, cured film, laminated body and semiconductor device
TWI835240B (en) Methods for manufacturing hardened materials, methods for manufacturing laminated bodies, methods for manufacturing semiconductor devices, and processing liquids
WO2021177263A1 (en) Photosensitive resin composition, method for producing pattern, photosensitive film, cured product, laminate, and device
WO2023120314A1 (en) Laminate, device, resin composition, method for manufacturing cured product, method for manufacturing laminate, and method for manufacturing device
TW202024786A (en) Photosensitive resin composition, cured film, layered product, production method for cured film, semiconductor device, and thermal base generator

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination