CN117083346A - Resin composition, cured product, laminate, method for producing cured product, and semiconductor device - Google Patents

Resin composition, cured product, laminate, method for producing cured product, and semiconductor device Download PDF

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Publication number
CN117083346A
CN117083346A CN202280025200.5A CN202280025200A CN117083346A CN 117083346 A CN117083346 A CN 117083346A CN 202280025200 A CN202280025200 A CN 202280025200A CN 117083346 A CN117083346 A CN 117083346A
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Prior art keywords
group
compound
resin composition
formula
acid
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CN202280025200.5A
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Chinese (zh)
Inventor
野崎敦靖
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/145—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing

Abstract

The present invention provides a resin composition, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and a semiconductor device containing the cured product or the laminate, wherein the resin composition contains a resin: which is a cyclized resin or precursor thereof; and a compound B represented by the formula (1-1), wherein X 1 Represents an n-valent linking group comprising an aromatic ring structure, X 1 At least 1 of the bonding sites with the nitrogen atom in the formula is an aromatic ring structure, R 1 Each independently represents a hydrogen atom or a 1-valent organic group, R 1 Can be combined with X 1 Bonding to form a ring structure, Y 1 Each independently represents an m+1 valent linking group, W 1 Respectively and independently representA group containing a polymerizable group, n represents an integer of 1 or more, and m represents an integer of 1 or more.

Description

Resin composition, cured product, laminate, method for producing cured product, and semiconductor device
Technical Field
The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, and a semiconductor device.
Background
Cyclized resins such as polyimide are excellent in heat resistance, insulation properties, and the like, and therefore can be used for various applications. The application is not particularly limited, and examples of the application include use of a material or a protective film as an insulating film or a sealing material when a semiconductor device for actual mounting is taken as an example. Further, the film can be used as a base film, a cover film, or the like of a flexible substrate.
For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing at least one of cyclized resins such as polyimide and precursors of cyclized resins.
Such a resin composition is applied to a substrate to form a photosensitive film by coating or the like, and then exposed to light, developed, heated or the like as necessary, whereby a cured product can be formed on the substrate.
The precursor of the cyclized resin such as a polyimide precursor is cyclized by heating, for example, to form a cyclized resin such as polyimide in a cured product.
The resin composition can be applied by a known coating method or the like, and therefore, it can be said that the resin composition is excellent in manufacturing suitability, for example, the shape, size, application position and the like of the applied resin composition are highly free in design and the like when applied. In addition to the high performance of the cyclized resin such as polyimide, the expansion of the application of the resin composition in industry is expected to be remarkable from the viewpoint of excellent suitability for such production.
For example, patent document 1 describes a photosensitive resin composition containing (a) an alkali-soluble polyimide and/or an alkali-soluble polyimide precursor, (b) a blocked isocyanate structure and a polymerizable compound having an unsaturated bond, (c) a photopolymerization initiator, and (d) a thermal crosslinking agent.
Patent document 2 describes a photosensitive composition containing a polyesteramic acid (a), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D), and a silane coupling agent (F).
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2009-009107
Patent document 2: japanese patent laid-open publication No. 2019-139091
Disclosure of Invention
Technical problem to be solved by the invention
In a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin, the obtained cured product is required to have excellent chemical resistance.
The present invention provides a resin composition which can obtain a cured product having excellent drug resistance, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and a semiconductor device containing the cured product or the laminate.
Means for solving the technical problems
Examples of representative embodiments of the present invention are shown below.
<1> a resin composition comprising:
resin: which is a cyclized resin or precursor thereof; a kind of electronic device with high-pressure air-conditioning system
A compound B represented by the formula (1-1),
[ chemical formula 1]
X 1 Represents an n-valent linking group comprising an aromatic ring structure, X 1 At least 1 of the bonding sites with the nitrogen atom in the formula is an aromatic ring structure, R 1 Each independently represents a hydrogen atom or a 1-valent organic group, R 1 Can be combined with X 1 Bonding to form a ring structure, Y 1 Each independently represents an m+1 valent linking group, W 1 Each independently represents a group containing a polymerizable group, n represents an integer of 1 or more, and m represents an integer of 1 or more.
<2> the resin composition according to <1>, wherein,
the content of the compound B is 1 mass% or more relative to the total mass of the resin composition.
<3> the resin composition according to <1> or <2>, further comprising a polymerizable compound different from the above-mentioned compound B.
<4> the resin composition according to <3>, wherein,
the content of the polymerizable compound is more than 0% by mass and not more than 20% by mass relative to the total mass of the composition.
<5> the resin composition according to any one of <1> to <4>, wherein,
the acid value of the resin is 1mmol/g or less.
<6> the resin composition according to any one of <1> to <5>, wherein,
the resin has a polymerizable group.
<7> the resin composition according to any one of <1> to <6>, wherein,
The molecular weight of the compound B is 1,000 or less.
<8> the resin composition according to any one of <1> to <7>, further comprising a polymerization initiator.
<9> the resin composition according to any one of <1> to <8>, wherein,
w in the above formula (1-1) 1 Is a radical polymerizable group.
<10> the resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a rewiring layer.
<11> a cured product obtained by curing the resin composition according to any one of <1> to <10 >.
<12> a laminate comprising 2 or more layers of the cured product of <11>, wherein any of the layers of the cured product comprises a metal layer between each other.
<13> a method for producing a cured product comprising a film formation step of applying the resin composition according to any one of <1> to <10> to a substrate to form a film.
<14> the method for producing a cured product according to <13>, comprising an exposure step of exposing the film and a developing step of developing the film.
<15> the method for producing a cured product according to <13> or <14>, comprising a heating step of heating the film at 50 to 450 ℃.
<16> a semiconductor device comprising the cured product of <11> or the laminate of <12 >.
Effects of the invention
According to the present invention, there are provided a resin composition which can give a cured product excellent in drug resistance, a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, and a semiconductor device comprising the cured product 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 illustrated embodiments.
In the present specification, the numerical range indicated by the symbol "to" refers to 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 "process" means a process which includes not only an independent process but also a process which cannot be clearly distinguished from other processes as long as the intended function of the process can be achieved.
In the labeling of groups (radicals) in the present specification, the label which is not labeled with a substituted or unsubstituted includes a group (radical) having no substituent, and includes a group (radical) having a substituent. For example, "alkyl" 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, unless otherwise specified, "exposure" includes not only exposure by light but also exposure by a particle beam such as an electron beam or an ion beam. Examples of the light used for exposure include an open line spectrum of a mercury lamp, an active ray such as extreme ultraviolet rays (EUV light), X-rays, and electron beams, and radiation, which are typified by excimer laser light.
In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", "(meth) acrylic" means either or both of "acrylic" and "methacrylic", and "(meth) acryl" means either or both of "acryl" and "methacryl".
In the present specification, me in the structural formula represents methyl, et represents ethyl, bu represents butyl, and Ph represents phenyl.
In the present specification, the total solid content refers to the total mass of the components other than the solvent among all the components of the composition. In the present specification, the solid content concentration is the mass percentage of the other components than the solvent with respect to the total mass of the composition.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by Gel Permeation Chromatography (GPC) and are defined as polystyrene equivalent values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) and connecting a protection column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION above) in series as a column. These molecular weights were measured using THF (tetrahydrofuran) as an eluent, unless otherwise specified. Among them, NMP (N-methyl-2-pyrrolidone) can be used when THF is not suitable as an eluent, for example, when solubility is low. Further, unless otherwise specified, a UV ray (ultraviolet ray) detector having a wavelength of 254nm is used for detection in GPC measurement.
In the present specification, when the positional relationship of each layer constituting the laminate is described as "up" or "down", it is sufficient that another layer exists above or below the layer serving as the reference among the layers concerned. That is, the 3 rd layer or the 3 rd element may be further interposed between the layer to be the reference and the other layer, and the layer to be the reference and the other layer do not need to be in contact. If not specifically described, the direction in which the base material layers are stacked is referred to as "up", or the direction from the base material toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down", when the resin composition layer is present. In addition, these vertical directions may be set for convenience in the present specification, and in a practical embodiment, the "upward" direction in the present specification may be oriented differently from the vertical direction.
In the present specification, unless otherwise specified, each component contained in the composition may contain 2 or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature was 23℃and the air pressure was 101,325Pa (1 air pressure), and the relative humidity was 50% RH.
In the present specification, a combination of preferred embodiments is a more preferred embodiment.
(resin composition)
The resin composition of the present invention comprises a resin which is a cyclized resin or a precursor thereof; and a compound B represented by the formula (1-1).
[ chemical formula 2]
X 1 Represents an n-valent linking group comprising an aromatic ring structure, X 1 At least 1 of the bonding sites with the nitrogen atom in the formula is an aromatic ring structure, R 1 Each independently represents a hydrogen atom or a 1-valent organic group, R 1 Can be combined with X 1 Bonding to form a ring structure, Y 1 Each independently represents an m+1 valent linking group, W 1 Each independently represents a polymer containing a polymerizable groupThe group, n, represents an integer of 1 or more, and m represents an integer of 1 or more.
The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and more preferably for forming a film for exposure and development using a developer containing an organic solvent.
The resin composition of the present invention can be used for, for example, forming an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like, and is preferably used for forming an interlayer insulating film for a rewiring layer.
The resin composition of the present invention can be used for forming a positive-type developing photosensitive film, or can be used for forming a negative-type developing photosensitive film, and is preferably used for forming a negative-type developing photosensitive film.
In the present invention, in exposure and development, negative development means development in which a non-exposed portion is removed by development, and positive development means development in which an exposed portion is removed by development.
As the exposure method, the developing solution, and the developing method, for example, the exposure method described in the exposure step described in the description of the method for producing a cured product, the developing solution described in the developing step, and the developing method described in the developing step can be used.
According to the resin composition of the present invention, a cured product having excellent drug resistance can be obtained.
The mechanism for obtaining the above effects is not clear, but is presumed as follows.
Conventionally, a cured product has been obtained using a composition containing a cyclized resin or a precursor thereof and a polymerizable compound.
The present inventors have found that the use of a polymerizable compound having a specific structure as a polymerizable compound in the present invention improves drug resistance.
This is presumably because, by blending the compound B having a urethane bond and a polymerizable group into the polymer, hydrogen bonds are formed between urethane bonds in the polymer or between urethane bonds and imide or amide sites in the polymer.
It is also considered that the cured film obtained by incorporating a urethane bond having a structure softer than that of an imide ring structure or the like into the above polymer is excellent in elongation at break.
Further, by introducing a urethane bond having a structure softer than an imide ring structure or the like into the polymer, the elastic modulus of the obtained cured film may be reduced, and the internal stress at the time of forming the cured film may be reduced, thereby suppressing warpage of the cured film.
Here, patent documents 1 and 2 do not describe the use of compound B.
The components contained in the resin composition of the present invention will be described in detail below.
< specific resin >
The resin composition of the present invention contains at least 1 resin (specific resin) selected from the group consisting of a cyclized resin and a precursor thereof.
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
In the present invention, the main chain means a relatively longest bonding chain in a resin molecule.
Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.
The precursor of the cyclized resin is a resin whose chemical structure is changed by an external stimulus to form a cyclized resin, preferably a resin whose chemical structure is changed by heat to form a cyclized resin, more preferably a resin whose ring structure is formed by a thermally generated ring-closure reaction.
Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.
That is, the resin composition of the present invention preferably contains at least 1 resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, polyamideimide and polyamideimide precursor as the specific resin.
The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin.
The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.
When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, more preferably contains a radical polymerization initiator described later and contains a radical crosslinking agent described later. If necessary, a sensitizer to be described later may be further contained. Such a resin composition of the present invention forms, for example, a negative photosensitive film.
The specific resin may have a polar conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described later. Such a resin composition of the present invention forms, for example, a chemically amplified positive photosensitive film or a chemically amplified negative photosensitive film.
When the specific resin has a polymerizable group, the resin preferably has a polymerizable group and a molecular chain containing a urea bond.
For example, the molecular chain is preferably bonded to the main chain of the resin as a side chain.
When the specific resin contains a repeating unit represented by the following formula (2), the molecular chain is preferably, for example, R contained in the repeating unit represented by the formula (2) 111 、R 115 、R 113 R is R 114 At least 1 of (3).
When the specific resin contains a repeating unit represented by the following formula (4), the molecular chain is preferably, for example, R contained in the repeating unit represented by the formula (4) 131 R is R 132 At least 1 of (3).
When the specific resin contains a repeating unit represented by the following formula (3), the molecular chain is preferably, for example, R contained in the repeating unit represented by the formula (3) 121 、R 122 、R 123 R is R 124 At least 1 of (3).
When the specific resin contains a repeating unit represented by the following formula (X), the molecular chain is preferably, for example, R contained in the repeating unit represented by the formula (X) 133 R is R 134 At least 1 of (3).
The specific resin comprisesIn the case of the repeating unit represented by the formula (PAI-2), the molecular chain is preferably, for example, R contained in the repeating unit represented by the formula (PAI-2) 111 、R 117 R is R 113 At least 1 of (3).
When the specific resin contains a repeating unit represented by the following formula (PAI-3), the above molecular chain is preferably, for example, R contained in the repeating unit represented by the formula (PAI-3) 111 R is R 117 At least 1 of (3).
The acid value of the specific resin is preferably 0mmol/g to 1.0mmol/g, more preferably 0mmol/g to 0.8mmol/g, and even more preferably 0mmol/g to 0.6mmol/g, from the viewpoint of chemical resistance.
The acid value is determined, for example, by JIS K0070: the method described in 1992.
Since the low-oxidability resin having an acid value in the above range has high permeability to alkali, the cured film using such a resin is less likely to be damaged by an alkaline chemical (e.g., tetramethylammonium hydroxide, etc.).
Further, it is considered that by using the compound B, hydrogen bonds of carbamates or carbamates with imide in the resin are formed in the cured film, and thus permeation of an organic solvent (for example, DMSO or the like) in the cured film is suppressed.
From the above, it is assumed that the combination of the resin having an acid value in the above range and the compound B improves the drug resistance. That is, it is considered that the use of the resin having an acid value in the above range in combination with the compound B in the resin composition makes the cured film obtained less susceptible to damage by the alkali or organic solvent contained in the developer or the like and the alkali or organic solvent contained in other compositions or the like.
[ polyimide precursor ]
The polyimide precursor used in the present invention is not particularly limited in kind and the like, and preferably contains a repeating unit represented by the following formula (2).
[ chemical formula 3]
In the formula (2), A 1 A is a 2 Each independently represents an oxygen atom or-NH-, R 111 Represents a 2-valent organic group, R 115 Represents a 4-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group.
A in formula (2) 1 A is a 2 Each independently represents an oxygen atom or-NH-, preferably an oxygen atom.
R in formula (2) 111 Represents a 2-valent organic group. Examples of the 2-valent organic group include a group 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 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination of these, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above-mentioned straight chain or branched aliphatic group may be substituted with a heteroatom-containing group, and the cyclic hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a heteroatom-containing group. As a preferred embodiment of the present invention, R can be exemplified 111 Is composed of-Ar-and-Ar-L-Ar-examples of the groups represented are those of the formula, particularly preferred are groups represented by-Ar-L-Ar-. Wherein Ar is an aromatic group, L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -or-NHCO-, or a group consisting of a combination of more than 2 of the above. The preferred ranges of these are as described above.
R 111 Preferably derived from diamines. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. The diamine may be used in an amount of 1 or 2 or more.
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 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination of these, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above-mentioned straight chain or branched aliphatic group may be substituted with a heteroatom-containing group, and the cyclic hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a heteroatom-containing group. Examples of the group containing an aromatic group include the following groups.
[ chemical formula 4]
Wherein A represents a single bond or a 2-valent linking group, 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-, -SO 2 -, -NHCO-or a combination of these, more preferably a single bond or an alkylene group selected from the group consisting of C1-3 which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-or-SO 2 The radicals in (E) -are further preferably-CH 2 -、-O-、-S-、-SO 2 -、-C(CF 3 ) 2 -or-C (CH) 3 ) 2 -。
Wherein, represents the bonding site with other structures.
Specific examples of the diamine include at least 1 diamine selected from the following: 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane or 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1, 2-1, 3-or 1, 4-diaminocyclohexane, 1,2, 1, 3-or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane, isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4' -or 3,3' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -or 3,3' -diaminodiphenylmethane, 4' -or 3,3' -diaminodiphenylsulfone, 4,4' -or 3,3' -diaminodiphenyl sulfide, 4' -or 3,3' -diaminobenzophenone, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dimethoxy-4, 4' -diaminobiphenyl, and 2, 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, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -diamino p-diphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (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' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3 '-diethyl-4, 4' -diaminodiphenyl methane 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane, 4 '-diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3',4,4 '-tetraminobiphenyl, 3',4 '-tetraminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4' -diaminobiphenyl, 9 '-bis (4-aminophenyl) fluorene, 4' -dimethyl-3, 3 '-diaminodiphenyl sulfone, 3',5 '-tetramethyl-4, 4' -diaminodiphenyl methane, 2, 4-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, bis (p-aminophenyl) octamethylpentasiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzol, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecanefluoroheptane, 2-bis [4- (3-aminophenyl) hexafiuorophenoxy ] propane, 2-5-diaminophenoxy ] hexafluoropropane, 2, 4-bis [ 2, 3-aminophenyl ] hexafluoropropane For bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl 4,4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 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', 6' -hexafluoro-tolidine, and 4,4' -diaminotetrabiphenyl.
Further, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International publication No. 2017/038598 are also preferable.
Further, diamines having 2 or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International publication No. 2017/038598 may be preferably used.
From the viewpoint of flexibility of the obtained organic film, R 111 Preferably represented by-Ar-L-Ar-. Wherein Ar is an aromatic group and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -0-, -CO-, -S-, -SO 2 -or-NHCO-, or a group consisting of a combination of more than 2 of the above. Ar is preferably a phenylene group which is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom-O-, -CO-, -S-or-SO 2 -. The aliphatic hydrocarbon group herein is preferably an alkylene group.
Moreover, from the viewpoint of the i-ray transmittance, R 111 The 2-valent organic group represented by the following formula (51) or (61) is preferable. In particular, from the viewpoints of i-ray transmittance and availability, the 2-valent organic group represented by formula (61) is more preferable.
(51)
[ chemical formula 5]
In the formula (51), R 50 ～R 57 Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R 50 ～R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and each independently represents a bonding site to a nitrogen atom in formula (2).
As R 50 ～R 57 Examples of the 1-valent organic group (1) include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
[ chemical formula 6]
In the formula (61), R 58 R is R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and each independently represents a bonding site to a nitrogen atom in formula (2).
Examples of the diamine having the structure of formula (51) or (61) 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 in combination of 2 or more kinds.
Moreover, from the viewpoint of the chemical resistance of the obtained cured film, R 111 A group represented by the following formula (R-1) is preferable.
[ chemical formula 7]
*-Ar 1 -O-Ar 2 -O-Ar 3 -* (R-1)
Ar in the formula (R-1) 1 ～Ar 3 Each independently represents an aryl group, and each represents a bonding site to a nitrogen atom in formula (2).
Ar in the formula (R-1) 1 Ar and Ar 3 Each independently is preferably an aromatic hydrocarbon group, more preferably a phenylene group, and further preferably a 1, 4-phenylene group. Ar (Ar) 1 Ar and Ar 3 Can be respectively and independentlyIs an aromatic heterocycle. Examples of the hetero atom contained in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. The aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring.
Ar in the formula (R-1) 2 A group represented by the following formula (AR 2-1) is preferable.
[ chemical formula 8]
In the formula (AR 2-1), ar in the formula (R-1) is represented by 1 Ar and Ar 3 Is bonded to the bonding site of the substrate.
In addition, ar 2 Can be as described above for Ar 1 The same groups.
R in formula (2) 115 Represents a 4-valent organic group. The 4-valent organic group is preferably a 4-valent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).
In the formula (5) or (6), each independently represents a bonding site to another structure.
[ chemical formula 9]
In the formula (5), R 112 Is a single bond or a 2-valent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom-O-, -CO-, -S-, -SO 2 -and-NHCO-, and combinations thereof, more preferably a single bond, selected from the group consisting of alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -CO-, -S-, and-SO 2 The radicals in are further preferably selected from the group consisting of-CH 2 -、-C(CF 3 ) 2 -、-C(CH 3 ) 2 -, -O-, -CO-; -S-and-SO 2 -a valence 2 group in (a).
Specifically, R 115 The tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride may be mentioned. As equivalent toR 115 The polyimide precursor may contain only 1 tetracarboxylic dianhydride residue or may contain 2 or more types.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
[ chemical formula 10]
In the formula (O), R 115 Represents a 4-valent organic group. R is R 115 R in the formula (2) 115 The meaning is the same, and the preferred ranges are also the same.
Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 7-naphthalene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalene tetracarboxylic dianhydride, 2',3,3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 1,2,4, 5-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,8,9, 10-phenanthrene tetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, and alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.
As a preferable example, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International publication No. 2017/038598 can be mentioned.
In the formula (2), R 111 R is R 115 At least one of them may further have an OH group. More specifically, as R 111 The residue of a bisaminophenol derivative may be mentioned.
R in formula (2) 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group. The 1-valent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxide group. Also, R is preferably 113 R is R 114 At least one of them comprises a polymerizable group, more preferably both comprise a polymerizable group. Also preferred is R 113 R is R 114 At least one of them contains 2 or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, a radical, or the like, and is preferably a 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, and an amino group. The radical polymerizable group of the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group or the like), (meth) acrylamide group, (meth) acryloyloxy group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III).
[ chemical formula 11]
In the formula (III), R 200 Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.
In formula (III), the bonding sites to other structures are represented.
In the formula (III), R 201 Represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, cycloalkylene or polyalkoxyene groups.
R 201 Preferred examples of (a) include an alkylene group such as a vinyl group, a propenyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, or a dodecamethylene group, a 1, 2-butanediyl group, a 1, 3-butanediyl group, -CH2CH (OH) CH2-, a polyalkoxy group, more preferably an alkylene group such as a vinyl group or a propenyl group, -CH2CH (OH) CH2-, a cyclohexyl group, or a polyalkoxy group, and still more preferably an alkylene group such as a vinyl group or a propenyl group, or a polyalkoxy group.
In the present invention, the polyalkoxylene group means a group in which 2 or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkylene groups contained in the polyalkylene oxide groups may be the same or different, respectively.
When the polyalkylene oxide group contains a plurality of alkylene oxide groups having different alkylene groups, the alkylene oxide groups in the polyalkylene oxide group may be arranged randomly, may have a block or may have an alternating pattern.
The number of carbon atoms of the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 6, still more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent. Preferred 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 further preferably 2 to 6.
The polyalkylene oxide group is preferably a group in which a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene group, a polytetramethylene group, or a plurality of ethylene oxide groups are bonded to a plurality of propylene oxide groups, more preferably a polyethylene oxide group or a polypropylene oxide group, and still more preferably a polyethylene oxide group, from the viewpoints of solvent solubility and solvent resistance. Among the groups in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. Preferred modes of repeating the number of ethyleneoxy groups and the like in these groups are as described above.
In the formula (2), R is 113 In the case of hydrogen atoms or R 114 In the case of a hydrogen atom, the polyimide precursor may form a conjugate salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
In the formula (2), R 113 R is R 114 At least one of them may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but is preferably an acetal group, a ketal group, a silicon-based ether group, a tertiary alkyl ester group, or the like, and more preferably an acetal group or a ketal group from the viewpoint of sensitivity to exposure.
Specific examples of the acid-decomposable group include a t-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a t-butoxycarbonylmethyl group, a trimethylsilyl ether group, and the like. Ethoxyethyl or tetrahydrofuranyl is preferred from the viewpoint of exposure sensitivity.
Furthermore, the polyimide precursor preferably has a fluorine atom in the structure. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.
In addition, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to a substrate. Specifically, as the diamine, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like can be mentioned.
The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least 1 of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-a). The amplitude of the exposure latitude can be further increased by including the repeating unit represented by the formula (2-a) in the polyimide precursor.
(2-A)
[ chemical formula 12]
In the formula (2-A), A 1 A is a 2 Represents an oxygen atom, R 111 R is R 112 Each independently represents a 2-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R 113 R is R 114 At least one of them is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.
A 1 、A 2 、R 111 、R 113 R is R 114 Independently of A in formula (2) 1 、A 2 、R 111 、R 113 R is R 114 The meaning is the same, and the preferred ranges are also the same.
R 112 R in formula (5) 112 The meaning is the same, and the preferred ranges are also the same.
The polyimide precursor may contain 1 kind of repeating unit represented by the formula (2), or may contain 2 or more kinds. Further, a structural isomer of the repeating unit represented by formula (2) may be contained. Furthermore, it is apparent that the polyimide precursor may contain other kinds of repeating units in addition to the repeating unit of the above formula (2).
As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol% or more based on the total repeating unit. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal may be the repeating unit represented by the formula (2).
The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 ～ 100,000, more preferably 10,000 ～ 50,000, and even more preferably 15,000 ～ 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.
The molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
In the present specification, the dispersity of the molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
When the resin composition contains a plurality of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least 1 polyimide precursor be within the above-mentioned ranges. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polyimide precursors as 1 resin are each within the above-mentioned ranges.
[ polyimide ]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly containing an organic solvent.
In the present specification, the alkali-soluble polyimide means a polyimide in which 0.1g or more of polyimide is dissolved in 100g of a 2.38 mass% aqueous tetramethylammonium solution at 23 ℃, and from the viewpoint of pattern formability, a polyimide in which 0.5g or more of polyimide is dissolved is preferable, and a polyimide in which 1.0g or more of polyimide is more preferable. The upper limit of the amount of dissolution is not particularly limited, but is preferably 100g or less.
Further, from the viewpoints of film strength and insulation properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
In the present specification, "main chain" means a relatively longest bonding chain among molecules of a polymer compound constituting a resin, and "side chain" means a bonding chain other than the above.
Fluorine atom-
From the viewpoint of film strength of the obtained organic film, the polyimide also preferably has fluorine atoms.
For example, R in the repeating unit represented by the following formula (4) is preferably a fluorine atom 132 Or R in the repeating unit represented by the following formula (4) 131 R contained as a fluorinated alkyl group in the repeating unit represented by the following formula (4) is more preferable 132 Or R in the repeating unit represented by the following formula (4) 131 。
The amount of fluorine atoms is preferably 5 mass% or more and preferably 20 mass% or less relative to the total mass of the polyimide.
Silicon atom-
From the viewpoint of film strength of the obtained organic film, the polyimide also preferably has silicon atoms.
The silicon atom is preferably R contained in the repeating unit represented by the following formula (4) 131 R contained in the repeating unit represented by the following formula (4) as the organomodified (poly) siloxane structure described later is more preferable 131 。
The silicon atom or the organomodified (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 1 mass% or more, more preferably 20 mass% or less, relative to the total mass of the polyimide.
Ethylenic unsaturation
From the viewpoint of the film strength of the obtained organic film, polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the terminal of the main chain, or may have an ethylenically unsaturated bond in a side chain, and preferably has an ethylenically unsaturated bond in a side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is preferably R contained in the repeating unit represented by the following formula (4) 132 Or R in the repeating unit represented by the following formula (4) 131 BetterR selected as a group having an ethylenically unsaturated bond to be contained in the repeating unit represented by the following formula (4) 132 Or R in the repeating unit represented by the following formula (4) 131 。
Wherein the ethylenically unsaturated bond is preferably R contained in the repeating unit represented by the following formula (4) 131 R contained in the repeating unit represented by the following formula (4) is more preferable as a group having an ethylenically unsaturated bond 131 。
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted, such as a vinyl group, an allyl group, or a vinylphenyl group, which is directly bonded to an aromatic ring, (meth) acrylamido group, (meth) acryloyloxy group, and a group represented by the following formula (IV).
[ chemical formula 13]
In the formula (IV), R 20 Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.
In the formula (IV), R 21 Represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C (=0) 0-, -0 (C=O) NH-, a (poly) alkyleneoxy group having 2 to 30 carbon atoms (alkylene group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3 carbon atoms, a repeating number of preferably 1 to 12, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) or a combination of 2 or more of these groups.
The alkylene group having 2 to 12 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof.
The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
Wherein R is 21 The group represented by any one of the following formulas (R1) to (R3) is preferable, and the group represented by the formula (R1) is more preferable.
[ chemical formula 14]
In the formulae (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group obtained by bonding these groups together in an amount of 2 or more, X represents an oxygen atom or a sulfur atom, X represents a bonding site to another structure, and ∈ represents R in the formula (IV) 21 Bonding sites for the bonded oxygen atoms.
In the formulae (R1) to (R3), a preferable mode of the alkylene group having 2 to 12 carbon atoms or the (poly) alkyleneoxy group having 2 to 30 carbon atoms in L is the same as that of the above-mentioned R 21 The preferred 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 modes are also the same.
The structure represented by the formula (R1) can be 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 or the like).
The structure represented by the formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenic unsaturated bond (for example, 2-hydroxyethyl methacrylate or the like).
The structure represented by the formula (R3) can be 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 or the like).
In formula (IV), the bond site to other structure is preferably a bond site to the main chain of polyimide.
The amount of the ethylenic unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.0005 to 0.05mol/g, relative to the total mass of the polyimide.
Polymerizable group other than group having ethylenic unsaturated bond
The polyimide may contain a polymerizable group other than the group having an ethylenically unsaturated bond.
Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.
For example, a polymerizable group other than the group having an ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the following formula (4) 131 。
The amount of the polymerizable group other than the group having an ethylenically unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.001 to 0.05mol/g, relative to the total mass of the polyimide.
Polarity-switching group-
The polyimide may have a polar conversion group such as an acid-decomposable group. Acid-decomposable groups in polyimide and R of the above formula (2) 113 R is R 114 The acid decomposable groups described in the above are the same, and the preferable modes are also the same.
The polarity-converting group is, for example, R contained in the repeating unit represented by the following formula (4) 131 、R 132 The ends of polyimide, and the like.
Acid number-
When the polyimide is used for alkali 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 polyimide is used for development (for example, the "solvent development" described later) using a developer mainly composed of an organic solvent, the acid value of polyimide is preferably 1 to 35mgKOH/g, more preferably 2 to 30mgKOH/g, and still more preferably 5 to 20mgKOH/g.
The acid value is measured by a known method, for example, by the method described in JIS K0070: the method in 1992.
The acid value of the polyimide is preferably 0 to 1.0mmol/g, more preferably 0 to 0.8mmol/g, and even more preferably Ommol/g to 0.6mmol/g, from the viewpoint of chemical resistance.
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.
pKa is a value that considers the dissociation reaction of hydrogen ions released by an acid and represents its equilibrium constant Ka by its negative common logarithmic pKa. In the present specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, reference may be made to the values described in the "reform 5 th edition chemical review base" by the japan chemical society.
In the case where the acid group is a polybasic acid such as phosphoric acid, the pKa is a first dissociation constant.
As such an acid group, the polyimide preferably contains at least 1 selected from a carboxyl group and a phenolic hydroxyl group, more preferably contains a phenolic hydroxyl group.
Phenolic hydroxyl radical-
From the viewpoint of making the development speed by the alkali developer appropriate, polyimide preferably has a phenolic hydroxyl group.
The polyimide may have a phenolic hydroxyl group at the terminal of the main chain or may have a phenolic hydroxyl group in a side chain.
The phenolic hydroxyl group is preferably R contained in the repeating unit represented by the following formula (4) 132 Or R in the repeating unit represented by the following formula (4) 131 。
The amount of the phenolic hydroxyl groups is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, relative to 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 structure, and preferably contains a repeating unit represented by the following formula (4).
[ chemical formula 15]
In the formula (4), R 131 Represents a 2-valent organic group, R 132 Represents a 4-valent organic group.
When the polymerizable group is present, the polymerizable group may be located at R 131 R is R 132 At least one of the above may be located at the terminal of polyimide as shown in the following formula (4-1) or formula (4-2).
(4-1)
[ chemical formula 16]
In the formula (4-1), R 133 The other groups are as defined for formula (4) and are polymerizable groups.
(4-2)
[ chemical formula 17]
R 134 R is R 135 At least one of them is a polymerizable group, and if not, an organic group, and the other groups have the same meaning as in formula (4).
Examples of the polymerizable group include a group containing the above-mentioned ethylenically unsaturated bond and a crosslinkable group other than the group containing the above-mentioned ethylenically unsaturated bond.
R 131 Represents a 2-valent organic group. As the 2-valent organic group, R in the formula (2) can be exemplified 111 The same groups, preferably the same ranges.
And as R 131 The diamine residue remaining after removal of the amino group of the diamine may be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic and aromatic diamines. Specific examples thereof include R in formula (2) of polyimide precursor 111 Is an example of (a).
From more effectively inhibiting the production during calcinationFrom the viewpoint of warp, R 131 Diamine residues having at least 2 alkylene glycol units in the backbone are preferred. More preferably, the diamine contains 2 or more ethylene glycol chains, propylene glycol chains, or both of them in total in one molecule, and still more preferably, the diamine contains no aromatic ring.
As diamines containing 2 or more ethylene glycol chains, propylene glycol chains, or both in total, there may be mentioned 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 Corporation), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like, but not limited thereto.
R 132 Represents a 4-valent organic group. As the 4-valent organic group, R in the formula (2) can be exemplified 115 The same groups, preferably the same ranges.
For example, as R 115 The 4 bonding bonds of the illustrated 4-valent organic group are bonded to 4-C (=o) -moieties in the above formula (4) to form a condensed ring.
And R is 132 The tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride may be mentioned. Specific examples thereof include R in formula (2) of polyimide precursor 115 Is an example of (a). From the viewpoint of the strength of the organic film, R 132 Preferably an aromatic diamine residue having 1 to 4 aromatic rings.
Also preferred is R 131 And R is 132 Having OH groups on at least one of them. More specifically, as R 131 Examples of the compounds include 2, 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, and the above-mentioned compounds (DA-1) to (DA-18) as R 132 The above-mentioned (DAA-1) to (DAA-5) are more preferable examples.
Furthermore, polyimide is also preferred to have fluorine atoms in the structure. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.
In addition, polyimide may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to a substrate. 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 resin composition, it is preferable that the main chain end of the polyimide is blocked with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, or reactive monoester compound. Among them, monoamines are more preferably used, and preferable examples of monoamines 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, 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-amino-phenol, 3-aminophenol, 4-aminophenol, and thiophenol. These may be used in an amount of 2 or more, or may be introduced into a plurality of different terminal groups by reacting a plurality of capping agents.
Imidization ratio (ring closure ratio)
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 viewpoints of film strength, insulation property, and the like of the obtained organic film.
The upper limit of the imidization ratio is not particularly limited, and may be 100% or less.
The imidization rate can be measured, for example, by the following method.
Measurement of aggregationThe infrared absorption spectrum of the imide was obtained to obtain 1377cm as an absorption peak derived from the imide structure -1 A nearby peak intensity P1. Next, the polyimide was heat-treated at 350℃for 1 hour, and then the infrared absorption spectrum was measured again to obtain 1377em -1 A nearby peak intensity P2. The imidization ratio of polyimide can be obtained by using the obtained peak intensities P1 and P2 according to the following formula.
Imidization ratio (%) = (peak intensity P1/peak intensity P2) ×100
The polyimide may have a polyimide composition comprising all 1R 131 Or R is 132 The repeating unit represented by the above formula (4) may have a structure comprising at least 2R's of different types 131 Or R is 132 The repeating unit represented by the above formula (4). The polyimide may contain a repeating unit represented by the above formula (4) or another kind of repeating unit. Examples of the other types of repeating units include repeating units represented by the above formula (2).
Polyimide can be synthesized, for example, as follows: the polyimide precursor is obtained by a method in which a tetracarboxylic dianhydride is reacted with a diamine (a part of which is substituted with a monoamine, i.e., a capping agent) at a low temperature, a method in which a tetracarboxylic dianhydride is reacted with a diamine (a part of which is substituted with an acid anhydride or a monoacylchloride compound or an active monoester compound, i.e., a capping agent) at a low temperature, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol and then reacted in the presence of a diamine (a part of which is substituted with a monoamine, i.e., a capping agent) and a condensing agent, a method in which the remaining dicarboxylic acid is subjected to an acyl chlorination with a diamine (a part of which is substituted with a monoamine, i.e., a capping agent) and then a method in which a part of the imide structure is introduced by a known imidization method or a method in which a part of the imide structure is stopped halfway is used, and a method in which a part of the imide structure is introduced by further mixing a fully imidized polymer and a polyimide precursor thereof. Further, other known polyimide synthesis methods can be applied. Further, other known polyimide synthesis methods can be applied.
The polyimide preferably has a weight average molecular weight (Mw) of 5,000 ～ 100,000, more preferably 10,000 ～ 50,000, and even more preferably 15,000 ～ 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties (for example, elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.
The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The molecular weight of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
When the resin composition contains a plurality of polyimides as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polyimide be in the above-mentioned range. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of kinds of polyimide as 1 kind of resin are each within the above-mentioned ranges.
[ polybenzoxazole precursor ]
The polybenzoxazole precursor used in the present invention is not particularly limited in its structure, and preferably contains a repeating unit represented by the following formula (3).
[ chemical formula 18]
In the formula (3), R 121 Represents a 2-valent organic group, R 122 Represents a 4-valent organic group, R 123 R is R 124 Each independently represents a hydrogen atom or a 1-valent organic group.
In the formula (3), R 123 R is R 124 Respectively with R in the formula (2) 113 The meaning is the same, and the preferred ranges are also the same. I.e. preferably at least oneThe latter is a polymerizable group.
In the formula (3), R 121 Represents a 2-valent organic group. The 2-valent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight chain aliphatic group is preferable. R is R 121 Dicarboxylic acid residues are preferred. The dicarboxylic acid residues may be used in an amount of 1 or 2 or more.
The dicarboxylic acid residue is preferably an aliphatic group-containing dicarboxylic acid or an aromatic group-containing dicarboxylic acid residue, and more preferably an aromatic group-containing dicarboxylic acid residue.
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, still more preferably 3 to 20, still more preferably 4 to 15, and particularly preferably 5 to 10. The straight chain aliphatic group is preferably an alkylene group.
As the dicarboxylic acid comprising a straight chain aliphatic group, examples thereof 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, and 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoro-adipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluoro-suberic acid, azelaic acid sebacic acid, hexadecanedioic acid, 1, 9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, ditridecanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, icosanedioic acid, triacontanedioic acid, tricosanedioic acid, diglycolic acid, dicarboxylic acids represented by the following formula, and the like.
[ chemical formula 19]
(wherein Z is a hydrocarbon group having 1 to 6 carbon atoms and n is an integer of 1 to 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 a group having the following aromatic group and 2-COOH is more preferable.
[ chemical formula 20]
Wherein A represents a member selected from the group consisting of-CH 2 -、-O-、-S-、-SO 2 -、-CO-、-NHCO-、-C(CF 3 ) 2 -and-C (CH) 3 ) 2 The 2-valent groups in (a) represent, independently of each other, bonding sites to other structures.
Specific examples of the dicarboxylic acid containing an aromatic group include 4,4 '-carbonyldibenzoic acid, 4' -dicarboxydiphenyl ether and terephthalic acid.
In the formula (3), R 122 Represents a 4-valent organic group. R in the above formula (2) is used as a 4-valent organic group 115 The meaning is the same, and the preferred ranges are also the same.
And R is 122 Preferable examples of the group derived from a bisaminophenol derivative include 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 4 '-diamino-3, 3' -dihydroxydiphenyl sulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, and, 2, 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 groups are preferable.
[ chemical formula 21]
Wherein X is 1 represents-O-, -S-, -C (CF) 3 ) 2 -、-CH 2 -、-SO 2 -, -NHCO-, and # each represent a bonding site to another structure. R represents a hydrogen atom or a 1-valent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. And R is 122 The structure represented by the above formula is also preferable. R is R 122 In the case of the structure represented by the above formula, a total of 4 are preferably any 2 of them are R in the formula (3) 122 The bonding site of the bonded nitrogen atom and the other 2 are R in the formula (3) 122 The bonding site of the bonded oxygen atom is more preferably 2 x is R in formula (3) 122 The bonding site of the bonded oxygen atom and 2# are R in formula (3) 122 The bonding site or 2 of the bonded nitrogen atoms is R in formula (3) 122 The bonding site of the bonded nitrogen atom and 2 # are R in formula (3) 122 The bonding site of the bonded oxygen atom is more preferably 2 x is R in formula (3) 122 The bonding site of the bonded oxygen atom and 2# are R in formula (3) 122 Bonding sites for the bonded nitrogen atoms.
The bisaminophenol derivative is also preferably a compound represented by the formula (A-s).
[ chemical formula 22]
In the formula (A-s), R 1 Is selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-; a single bond or an organic group in the following formula (A-sc). R is R 2 The hydrogen atom, alkyl group, alkoxy group, acyloxy group, and cyclic alkyl group may be the same or different. R is R 3 The hydrogen atom, the linear or branched alkyl group, the alkoxy group, the acyloxy group, or the cyclic alkyl group may be the same or different.
[ chemical formula 23]
(in the formula (A-sc): represents an aromatic ring bond with an aminophenol group of the bisaminophenol derivative represented by the formula (A-s))
It is considered that in the above formula (A-s), the amino group is further located at the ortho position to the phenolic hydroxyl group, i.e., at R 3 The substituent is particularly preferable in that the distance between the carbonyl carbon of the amide bond and the hydroxyl group is closer, and the effect of increasing the cyclization ratio at the time of curing at low temperature is further improved.
In the above formula (A-s), R 2 Is alkyl and R 3 In the case of an alkyl group, the effect of high transparency to i-rays and high cyclization ratio when cured at low temperature can be maintained, and thus is preferable.
In the above formula (A-s), R 1 Further preferred is an alkylene group or a substituted alkylene group. As R 1 Specific examples of the alkylene group and substituted alkylene group include straight-chain or branched alkyl groups having 1 to 8 carbon atoms, wherein a polyphenyl having sufficient solubility in a solvent and excellent balance can be obtained while maintaining the effects of high transparency to i-rays and high cyclization ratio at the time of curing at low temperatureFrom the viewpoint of the benzoxazole precursor, more preferable is-CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -。
Examples of the production method of the bisaminophenol derivative represented by the formula (A-s) include paragraphs 0085 to 0094 and example 1 (0189 to 0190) of Japanese unexamined patent publication No. 2013-256506, which are incorporated herein by reference.
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. Of course, these are not limiting.
In addition to the repeating units of formula (3) above, the polybenzoxazole precursor may also contain other types of repeating units.
From the viewpoint of being able to suppress warpage accompanying closed-loop generation, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another kind of repeating unit.
[ chemical formula 24]
In the formula (SL), Z has a structure a and a structure b, R 1s Is hydrogen atom or hydrocarbon group with 1-10 carbon atoms, R 2s Is a hydrocarbon group of 1 to 10 carbon atoms, R 3s 、R 4s 、R 5s 、R 6s At 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 and b structures may be block polymerization or random polymerization. Regarding the mole% of the Z moiety, the a structure is 5 to 95 mole%, the b structure is 95 to 5 mole%, and a+b is 100 mole%.
In the formula (SL), preferable Z is R in the b structure 5s R is R 6s Is an example of a phenyl group. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight as described aboveThe range can effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and can achieve both the effect of suppressing warpage and the effect of improving solvent solubility.
When the diamine residue represented by the formula (SL) is contained as another type of repeating unit, it is preferable that the diamine residue further contains a tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic acid dianhydride as a repeating unit. Examples of such tetracarboxylic acid residues include R in formula (2) 115 Is an example of (a).
For example, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 ～ 30,000, more preferably 20,000 ～ 29,000, and further preferably 22,000 ～ 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 molecular weight dispersity of the polybenzoxazole precursor is not particularly limited, and is, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, still more preferably 2.3 or less, and still more preferably 2.2 or less.
When the resin composition contains a plurality of polybenzoxazole precursors as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polybenzoxazole precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polybenzoxazole precursors as 1 resin are each within the above ranges.
[ 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), more preferably a compound represented by the following formula (X) and having a polymerizable group. The polymerizable group is preferably a radical polymerizable group. Further, the compound may be a compound represented by the following formula (X) and having a polar conversion group such as an acid-decomposable group.
[ chemical formula 25]
In the formula (X), R 133 Represents a 2-valent organic group, R 134 Represents a 4-valent organic group.
When the polar group such as a polymerizable group or an acid-decomposable group is present, the polar group such as a polymerizable group or an acid-decomposable group may be present at R 133 R is R 134 At least one of the above may be located at the terminal of polybenzoxazole as shown by the following formula (X-1) or formula (X-2).
(X-1)
[ chemical formula 26]
In the formula (X-1), R 135 R is R 136 At least one of them is a polar conversion group such as a polymerizable group or an acid-decomposable group, and if it is not a polar conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups have the same meaning as in formula (X).
(X-2)
[ chemical formula 27]
In the formula (X-2), R 137 The other groups are as defined for formula (X) and the rest are substituents which are polar conversion groups such as polymerizable groups or acid-decomposable groups.
The polar conversion group such as a polymerizable group or an acid-decomposable group is the same as the polymerizable group described in the polymerizable group of the polyimide precursor.
R 133 Represents a 2-valent organic group. Examples of the 2-valent organic group include an aliphatic group and an aromatic group. As a specific example, a polybenzo can be givenR in formula (3) of the oxazole precursor 121 Is an example of (a). Further, the preferable examples and R 121 The same applies.
R 134 Represents a 4-valent organic group. Examples of the 4-valent organic group include R in formula (3) of the polybenzoxazole precursor 122 Is an example of (a). Further, the preferable examples and R 122 The same applies.
For example, as R 122 The 4 bonding bonds of the illustrated 4-valent organic group are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, R 134 In the case of the following organic group, the following structure is formed. In the following structures, the bonding sites with nitrogen or oxygen atoms in formula (X) are represented, respectively.
[ chemical formula 28]
The oxazolization ratio of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited and may be 100%. When the rate of the oxazolization is 85% or more, the film shrinkage due to the closed loop occurring when the film is oxazolized by heating is reduced, and thus the occurrence of warpage can be effectively suppressed.
For example, the above-mentioned oxazolification rate can be measured by the following method.
The infrared absorption spectrum of polybenzoxazole was measured to obtain 1650cm as an absorption peak of the amide structure derived from the precursor -1 A nearby peak intensity Q1. Next, the film is used at 1490cm -1 The absorption intensity of the aromatic ring observed nearby was normalized. After the polybenzoxazole precursor was heat-treated at 350℃for 1 hour, the infrared absorption spectrum was measured again to obtain 1650cm -1 The peak intensity Q2 in the vicinity was measured at 1490cm -1 The absorption intensity of the aromatic ring observed nearby was normalized. Using the normalized values of the obtained peak intensities Q1, Q2, the oxazolization ratio of the polybenzoxazole can be obtained according to the following formula.
Oxazolification rate (%) = (normalized value of peak intensity Q1/normalized value of peak intensity Q2) ×100
Polybenzoxazole can have a structure containing all 1R 131 Or R is 132 The repeating unit of the above formula (X) may have at least 2R's of different types 131 Or R is 132 The repeating unit of formula (X) above. The polybenzoxazole may contain a repeating unit of other types in addition to the repeating unit of the above formula (X).
For example, a bisaminophenol derivative is reacted with a compound comprising R 133 The polybenzoxazole precursor is obtained by reacting a dicarboxylic acid selected from the dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acids, and the like, and then oxazolized by a known oxazolization reaction method.
In the case of dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1, 2, 3-benzotriazole or the like in advance may be used in order to improve the reaction yield or the like.
The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 ～ 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical characteristics, 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.
The number average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The molecular weight of the polybenzoxazole has a dispersity of preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole is not particularly limited, and 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.
When the resin composition contains a plurality of polybenzoxazoles as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polybenzoxazole be within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polybenzoxazoles as 1 resin are each within the above-mentioned ranges.
[ Polyamide imide precursor ]
The polyamideimide precursor preferably comprises a repeating unit represented by the following formula (PAI-2).
[ chemical formula 29]
In the formula (PAI-2), R 117 Represents a 3-valent organic group, R 111 Represents a 2-valent organic group, A 2 Represents an oxygen atom or-NH-, R 113 Represents a hydrogen atom or a 1-valent organic group.
In the formula (PAI-2), R 117 Examples of the group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group in which these groups are linked by a single bond or a linking group to 2 or more, preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a group in which these groups are combined by a single bond or a linking group to 2 or more, more preferably an aromatic group having 6 to 20 carbon atoms, and a group in which aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group to 2 or more.
As the above-mentioned linking group, a compound having a hydroxyl group, preferably-O-, -S-; -C (=o) -, -S (=o) 2 -, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these groups, more preferably-O-, -S-, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, and may be substituted with a halogen atom, preferably with all hydrogen atoms. Examples of the preferred halogenated alkylene group include (bistrifluoromethyl) methylene.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1, 3-phenylene group or a 1, 4-phenylene group.
And R is 117 Preferably from tricarboxylic acid compounds in which at least 1 carboxyl group can be halogenated. As the above halogenation, chlorination is preferable.
In the present invention, a compound having 3 carboxyl groups is referred to as a tricarboxylic acid compound.
2 carboxyl groups among 3 carboxyl groups of the above-mentioned tricarboxylic acid compound may be anhydrated.
Examples of the tricarboxylic acid compound which may be halogenated for producing the polyamideimide precursor include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds.
Only 1 kind of these tricarboxylic acid compounds may be used, or 2 or more kinds may be used.
Specifically, as the tricarboxylic acid compound, a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining 2 or more of these groups by a single bond or a linking group is preferable, and a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining 2 or more of aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group is more preferable.
Further, specific examples of the tricarboxylic acid compound include 1,2, 3-propane tricarboxylic acid, 1,3, 5-Pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3, 6-naphthalene tricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid by means of single bonds, -O-, -CH 2 -、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -、-SO 2 Or a compound in which phenylene groups are bonded.
These compounds may be those obtained by anhydrating 2 carboxyl groups (for example, trimellitic anhydride), or those obtained by halogenating at least 1 carboxyl group (for example, trimellitic anhydride chloride).
In the formula (PAI-2), R 111 、A 2 、R 113 Respectively with R in the above formula (2) 111 、A 2 、R 113 The meaning is the same, and the preferred mode is the same.
The polyamideimide precursor may further comprise other repeating units.
Examples of the other repeating unit include a repeating unit represented by the above formula (2), a repeating unit represented by the following formula (PAI-1), and the like.
[ chemical formula 30]
In the formula (PAI-1), R 116 Represents a 2-valent organic group, R 111 Represents a 2-valent organic group.
In the formula (PAI-1), R 116 Examples of the group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group in which these groups are linked by a single bond or a linking group to 2 or more, preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a group in which these groups are combined by a single bond or a linking group to 2 or more, more preferably an aromatic group having 6 to 20 carbon atoms, and a group in which aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group to 2 or more.
As the above-mentioned linking group, a compound having a hydroxyl group, preferably-O-, -S-; -C (=o) -, -S (=o) 2 -, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these groups, more preferably-O-, -S-, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, and may be substituted with a halogen atom, preferably with all hydrogen atoms. Examples of the preferred halogenated alkylene group include (bistrifluoromethyl) methylene.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1, 3-phenylene group or a 1, 4-phenylene group.
And R is 116 Preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having 2 carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having 2 halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound.
The carboxyl groups in the dicarboxylic acid dihalide compound may be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated for producing the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound, and the like.
These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used in an amount of 1 or 2 or more.
Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining 2 or more of these groups by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms or a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a group obtained by combining 2 or more of aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.
Further, as a specific example of the dicarboxylic acid compound, examples thereof 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, and 2, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoro adipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluoro suberic acid, azelaic acid, sebacic acid, hexadecyl sebacic acid, 1, 9-azelaic acid, dodecanedioic acid tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, hencanedioic acid, docanedioic acid, ditridecanedioic acid, ditetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, icosanedioic acid, triacontanedioic acid, triamcinolone diacid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4' -biphenylcarboxylic acid, 4' -dicarboxyl diphenyl ether, benzophenone-4, 4' -dicarboxylic acid, and the like.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which 2 carboxyl groups in specific examples of the above dicarboxylic acid compound are halogenated.
In the formula (PAI-1), R 111 R is the same as R in the above formula (2) 111 The meaning is the same, and the preferred mode is the same.
Furthermore, the polyamideimide precursor preferably also has a fluorine atom in the structure. The fluorine atom content in the polyamideimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.
In addition, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to a substrate. Specifically, as the diamine component, there may be mentioned a method using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like.
One embodiment of the polyamideimide precursor in the present invention includes a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) in a total amount of 50 mol% or more based on the total repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamideimide precursor other than the terminal may be any one of the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1) and the repeating unit represented by the formula (2).
In addition, another embodiment of the polyamideimide precursor in the present invention includes a structure in which the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamideimide precursor other than the terminal may be any of the repeating units represented by the formula (PA 1-2) or the repeating units represented by the formula (PAI-1).
The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 ～ 500,000, more preferably 5,000 ～ 100,000, and even more preferably 10,000 ～ 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.
The molecular weight of the polyamideimide precursor has a dispersity of preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersivity of the polyamideimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. When the resin composition contains a plurality of polyamide-imide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least 1 polyamide-imide precursor are within the above-mentioned ranges. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated as 1 resin of the plurality of polyamide-imide precursors are each within the above-mentioned ranges.
[ Polyamide imide ]
The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide which is soluble in a developer containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyamideimide means a polyamideimide in which 0.1g or more, preferably 0.5g or more, more preferably 1.0g or more, of the polyamideimide is dissolved in 100g of a 2.38 mass% aqueous tetramethylammonium solution at 23 ℃. The upper limit of the amount of dissolution is not particularly limited, but is preferably 100g or less.
In addition, from the viewpoints of film strength and insulation properties of the obtained organic film, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.
Fluorine atom-
From the viewpoint of film strength of the obtained organic film, the polyamideimide preferably has fluorine atoms.
The fluorine atom is preferably R contained in the repeating unit represented by the following formula (PAI-3) 117 Or R is 111 R contained as a fluorinated alkyl group in a repeating unit represented by the following formula (PAI-3) is more preferable 117 Or R is 111 。
The amount of fluorine atoms is preferably 5 mass% or more and preferably 20 mass% or less relative to the total mass of the polyamideimide.
Ethylenic unsaturation
From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond.
The polyamideimide may have an ethylenically unsaturated bond at the terminal of the main chain, or may have a side chain, preferably a side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is preferably R contained in the repeating unit represented by the following formula (PAI-3) 117 Or R is 111 R contained in the repeating unit represented by the following formula (PAI-3) is more preferable as a group having an ethylenically unsaturated bond 117 Or R is 111 。
The preferable mode of the group having an ethylenically unsaturated bond is the same as that of the group having an ethylenically unsaturated bond in the above polyimide.
The amount of the ethylenic unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.001 to 0.05mol/g, relative to the total mass of the polyamideimide.
Polymerizable group other than ethylenic unsaturated bond
The polyamideimide may have a polymerizable group other than an ethylenically unsaturated bond.
Examples of the polymerizable group other than an ethylenic unsaturated bond in the polyamide imide include the same groups as those of the polymerizable group other than an ethylenic unsaturated bond in the polyimide.
For example, the polymerizable group other than an ethylenically unsaturated bond is preferably R contained in the repeating unit represented by the formula (PAI-3) described later 111 。
The amount of the polymerizable group other than an ethylenic unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, relative to the total mass of the polyamideimide.
Polarity-switching group-
The polyamideimide may have a polar conversion group such as an acid-decomposable group. Acid-decomposable groups in the polyamideimide and R of the above formula (2) 113 R is R 114 The acid decomposable groups described in the above are the same, and the preferable modes are also the same.
Acid number-
When the polyamideimide is used for alkali development, the acid value of the polyamideimide 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 polyamideimide is used for development (for example, the "solvent development" described later) using a developing solution containing an organic solvent as a main component, the acid value of the polyamideimide is preferably 2 to 35mgKOH/g, more preferably 3 to 30mgKOH/g, and still more preferably 5 to 20mgKOH/g.
The acid value of the polyamide-imide is preferably 0mmol/g to 1.2mmol/g, more preferably 0mmol/g to 0.8mmol/g, still more preferably 0mmol/g to 0.6mmol/g, from the viewpoint of chemical resistance.
The acid value is measured by a known method, for example, by the method described in JIS K0070: the method in 1992.
The acid groups contained in the polyamide-imide include the same groups as the acid groups contained in the polyimide, and the preferable embodiments are also the same.
Phenolic hydroxyl radical-
From the viewpoint of making the development speed by the alkali developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.
The polyamideimide may have a phenolic hydroxyl group at the terminal of the main chain or may have a side chain.
The phenolic hydroxyl group is preferably contained in, for example, R in the repeating unit represented by the following formula (PAI-3) 117 Or R is 111 。
The amount of the phenolic hydroxyl groups is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, relative to the total mass of the polyamideimide.
The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, and preferably contains a repeating unit represented by the following formula (PAI-3).
[ chemical formula 31]
In the formula (PAI-3), R 111 R is R 117 Respectively with R in the formula (PAI-2) 111 R is R 117 The meaning is the same, and the preferred mode is the same.
When the polymerizable group is present, the polymerizable group may be located at R 111 R is R 11 At least one of w may be located at the terminal of the polyamideimide.
In order to improve the storage stability of the resin composition, it is preferable that the main chain end of the polyamide-imide is blocked with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, or an active monoester compound. The preferable mode of the blocking agent is the same as that of the blocking agent in the polyimide described above.
Imidization ratio (ring closure ratio)
The imidization rate (also referred to as "ring closure rate") of the polyamideimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more from the viewpoints of film strength, insulation property, and the like of the obtained organic film.
The upper limit of the imidization ratio is not particularly limited, and may be 100% or less.
The imidization ratio can be measured by the same method as the ring closure ratio of the polyimide.
Polyamide imideThe amine may have a structure comprising all 1R 111 Or R is 117 The repeating unit represented by the above formula (PAI-3) may have a structure comprising at least 2R 131 Or R is 132 The repeating unit represented by the above formula (PAI-3). The polyamideimide may contain a repeating unit represented by the above formula (PAI-3) and other types of repeating units. Examples of the other type of repeating unit include a repeating unit represented by the above formula (PAI-1) or formula (PAI-2).
The polyamideimide can be synthesized, for example, by the following method: the polyamide-imide precursor is obtained by a known method, and is synthesized by a known method of imidizing completely by a known imidization method or by a method of introducing a part of imide structure by stopping imidization halfway, or by a method of introducing a part of imide structure by further mixing a completely imidized polymer with the polyamide-imide precursor.
The weight average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further preferably 10,000 ～ 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical characteristics, the weight average molecular weight is particularly preferably 20,000 or more.
The number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
The molecular weight of the polyamideimide precursor has a dispersity of preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
When the resin composition contains a plurality of polyamide-imides as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polyamide-imide are within the above-mentioned ranges. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated from the plurality of polyamide-imide as 1 resin are each within the above-mentioned ranges.
[ method for producing polyimide precursor and the like ]
For example, a polyimide precursor or the like can be obtained by the following method: a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature to obtain a polyamic acid and esterifying with a condensing agent or an alkylating agent, a method of reacting a tetracarboxylic dianhydride with an alcohol in the presence of a diamine and a condensing agent after obtaining a diester from a tetracarboxylic dianhydride and an alcohol, a method of halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine after obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and the like. Among the above production methods, more preferable is a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated with a halogenating agent and reacted with a diamine. Among the above production methods, more preferred is a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated with a halogenating agent and reacted with a diamine.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole, N' -disuccinimide carbonate, and trifluoroacetic anhydride.
Examples of the alkylating agent include N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphoryl chloride.
In the method for producing a polyimide precursor or the like, an organic solvent is preferably used in the reaction. The organic solvent may be 1 or 2 or more.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ -butyrolactone, which are appropriately determined according to the raw materials.
In the method for producing a polyimide precursor or the like, an alkali compound is preferably added at the time of the reaction. The number of the basic compounds may be 1 or 2 or more.
The basic compound can be appropriately determined depending on the starting materials, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, N-dimethyl-4-aminopyridine, and the like.
Blocking agent-
In order to further improve the storage stability in the production of a polyimide precursor or the like, it is preferable to cap a carboxylic acid anhydride, an acid anhydride derivative, or an amino group remaining at the end of a resin such as a polyimide precursor. When the carboxylic acid anhydride and acid anhydride derivative remaining at the end of the resin are blocked, examples of the blocking agent include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like, and from the viewpoints of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferably used. Preferred examples of the monoalcohol include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, tertiary alcohols such as t-butanol, adamantanol, and the like. Preferred examples of the phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Further, preferable examples of monoamines 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, 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-aminophenol, 3-aminophenol, thiophenol, and the like. These may be used in an amount of 2 or more, or may be introduced into a plurality of different terminal groups by reacting a plurality of capping agents.
In addition, when the amino group at the end of the resin is blocked, the blocking can be performed with a compound having a functional group reactive with the amino group. The preferable blocking agent for the amino group is preferably carboxylic anhydride, carboxylic chloride, carboxylic bromide, sulfonic chloride, sulfonic anhydride, sulfonic carboxylic anhydride or the like, more preferably carboxylic anhydride or carboxylic chloride. Preferred examples of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2, 3-dicarboxylic anhydride. Preferred compounds of carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, benzoyl chloride, and the like.
Solid precipitation-
The production of the polyimide precursor and the like may include a solid precipitation step. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid is filtered as needed, and then the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol or a mixed liquid thereof, and the polymer component is precipitated, whereby the polymer component is precipitated as a solid and dried to obtain a polyimide precursor or the like. In order to improve the purification degree, operations such as redissolution, reprecipitation, precipitation, and drying may be repeated for the polyimide precursor or the like. The method may further comprise a step of removing ionic impurities using an ion exchange resin.
[ content ]
The content of the specific resin in the resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, and still more preferably 50 mass% or more, relative to the total solid content of the resin composition. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, 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 resin composition.
The resin composition of the present invention may contain only 1 specific resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
Furthermore, the resin composition of the present invention preferably further comprises at least 2 resins.
Specifically, the resin composition of the present invention may contain 2 or more types of specific resins and other resins described later in total, or may contain 2 or more types of specific resins, and preferably contains 2 or more types of specific resins.
When the resin composition of the present invention contains 2 or more specific resins, it is preferable that the resin composition contains a dianhydride-derived structure (R in the above formula (2)) 115 ) Different polyimide precursors of 2 or more types.
< other resins >
The resin composition of the present invention may contain the above specific resin and another resin (hereinafter, also simply referred to as "another resin") different from the specific resin.
Examples of the other resin include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth) acrylic resins, (meth) acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.
For example, by further adding a (meth) acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained.
For example, the resin composition may be prepared by adding a resin having a weight average molecular weight of 20,000 or less and a high value of the polymerizable group (for example, 1X 10 in 1g of the resin having a molar amount of the polymerizable group) -3 Molar ratio of (meth) acrylic resin of at least one molar ratio), the coatability of the resin composition, the solvent resistance of the pattern (cured product), and the like can be improved.
When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 1 mass% or more, still more preferably 2 mass% or more, still more preferably 5 mass% or more, and still more preferably 10 mass% or more, based on the total solid content of the resin composition.
The content of the other resin in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, still more preferably 70 mass% or less, still more preferably 60 mass% or less, and still more preferably 50 mass% or less, based on the total solid content of the resin composition.
In addition, as a preferred embodiment of the resin composition of the present invention, the content of other resins may be reduced. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0 mass% or more.
The resin composition of the present invention may contain only 1 kind of other resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
< Compound B >
The resin composition of the present invention contains a compound B represented by the formula (1-1).
[ chemical formula 32]
X 1 Represents an n-valent linking group comprising an aromatic ring structure, X 1 At least 1 of the bonding sites with the nitrogen atom in the formula is an aromatic ring structure, R 1 Each independently represents a hydrogen atom or a 1-valent organic group, R 1 Can be combined with X 1 BondingTo form a ring structure, Y 1 Each independently represents an m+1 valent linking group, W 1 Each independently represents a group containing a polymerizable group, n represents an integer of 1 or more, and m represents an integer of 1 or more.
〔X 1 〕
In the formula (1-1), X 1 The aromatic ring structure may be contained only in 1 or may be contained in 2 or more. As X 1 The aromatic ring structure in (a) may be an aromatic hydrocarbon ring structure or an aromatic heterocyclic structure, and is preferably an aromatic hydrocarbon ring structure, more preferably an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, and still more preferably a benzene ring structure. Examples of the hetero atom in the aromatic heterocyclic structure include an oxygen atom, a sulfur atom, and a nitrogen atom. And X is 1 The aromatic ring structure of (b) may further have a known substituent such as an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a vinyl group, a halogen atom, or the like.
When n is an integer of 2 or more, X 1 At least 1 of the bonding sites with the nitrogen atom in the formula (1-1) may be an aromatic ring structure, X 1 The mode in which all bonding sites with nitrogen atoms in the formula (1-1) are aromatic ring structures is also one of preferred modes of the present invention.
In the formula (1-1), X 1 Preferably an aromatic ring structure, or a hydrocarbon group with a moiety selected from the group consisting of-O-, -C (=O) -, -S (=O) 2 -and-NR N The group represented by the combination of at least 1 groups in (a) and containing at least 1 aromatic ring structure, more preferably an aromatic ring structure, or a group represented by the combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-and-C (=o) -and containing at least 1 aromatic ring structure, still more preferably a group represented by the following formula (X-1) or formula (X-2). R is R N Each independently represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
[ chemical formula 33]
In the formula (X-1), n is an integer identical to n in the formula (1-1), R X A represents an integer of 0 to 6-n, and a represents a bonding site to a nitrogen atom in formula (1-1).
In the formula (X-2), n1 and n2 each independently represent an integer of 1 to 4, n1+n2 is an integer identical to n in the formula (1-1), R X Each independently represents a substituent, L 1 Represents a single bond or a 2-valent linking group, b represents an integer of 0 to 5-n inclusive, c represents an integer of 0 to 5-n inclusive, and x represents a bonding site to a nitrogen atom in formula (1-1).
In the formula (X-1), n is preferably an integer of 1 to 4, more preferably 1 or 2. The mode in which n is 1 is also one of preferred modes of the present invention.
In the formula (X-1), R X The substituent is not particularly limited, and a known substituent may be used, and examples thereof include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a vinyl group, a halogen atom, etc., preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a vinyl group, or a phenyl group, more preferably a methyl group, a methoxy group, a vinyl group, or a phenyl group.
In the formula (X-1), a is preferably an integer of 0 to 2, more preferably 0 or 1.
In the formula (X-2), n1 is preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1.
In the formula (X-2), n2 is preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1.
In the formula (X-2), R X And R in formula (X-1) X The meaning is the same, and the preferred mode is the same.
In the formula (X-2), L 1 Preferably a single bond, a hydrocarbyl, -O-, -C (=o) -, -S-, or-S (=o) 2 -, more preferably a single bond, an alkyl group or a phenylene group, still more preferably a single bond or an alkyl group having 1 to 4 carbon atoms, particularly preferably a single bond or a methylene group.
In the formula (X-2), b is preferably an integer of 0 to 2, more preferably 0 or 1.
In the formula (X-2), c is preferably an integer of 0 to 2, more preferably 0 or 1.
X is shown below 1 But is not limited to this. In the following specific examples, the bonding site to the nitrogen atom in formula (1-1) is shown.
[ chemical formula 34]
In the formula (1-1), R 1 Each independently is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom. And R is 1 Can be combined with X 1 Bonding to form a ring structure, for example, X 1 Aromatic ring structure and R 1 Bonding mode. The ring structure formed may be an indoline ring structure or the like.
〔Y 1 〕
In the formula (1-1), Y 1 Preferably a hydrocarbyl group or a hydrocarbyl group with a moiety selected from the group consisting of-O-, -C (=o) -, -S (=o) 2 -and-NR N More preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -C (=O) -and-NR N -a group represented by a combination of at least 1 of the groups. R is R N As described above.
The hydrocarbon group may be any one of an aromatic hydrocarbon group and an aliphatic hydrocarbon group, Y 1 Preferably at least an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group.
Further, from the viewpoint of chemical resistance, Y 1 Also preferably contains urea linkages, urethane linkages or amide linkages. Y is Y 1 When the urethane bond or the amide bond is contained, the orientation of the urethane bond or the amide bond is not particularly limited. For example, Y 1 As the structure containing a urethane bond, a group represented by the following formula (Y-1) may be contained.
[ chemical formula 35]
In the formula (Y-1), X represents a compound comprisingA 1-valent group of an aromatic ring structure, wherein at least 1 of bonding sites with nitrogen atoms in the formula in X is an aromatic ring structure, R 1 Represents a hydrogen atom or a 1-valent organic group, R 1 May bond to X to form a ring, and represents a bonding site to other structures.
In the formula (Y-1), preferred modes of X are the same as those of X in the formula (1-1) when n is 1 1 The same is preferable.
In the formula (Y-1), R 1 R in formula (1-1) 1 The same is preferable.
Y is shown below 1 But is not limited to this. In the following embodiment, # represents a bonding site to an oxygen atom in formula (1-1), and W 1 Is bonded to the bonding site of the substrate.
[ chemical formula 36]
〔W 1 〕
In the formula (1-1), W 1 Is a group comprising a polymerizable group.
As W 1 The polymerizable group in (a) may be a radical polymerizable group, an epoxy group, an oxetanyl group, a hydroxymethyl group, an alkoxymethyl group or the like, and a radical polymerizable group is preferable.
Examples of the radical polymerizable group include a (meth) acryloyloxy group, a (meth) acrylamide group, a vinylphenyl group, a styryl group, a vinyl group, an allyl group, and a maleimide group.
As W 1 (meth) acryloyloxy, (meth) acrylamido, vinylphenyl, vinylphenoxy, styryl, vinyl ether, allyl ether, maleimide, more preferably (meth) acryloyloxy, (meth) acrylamido or maleimide.
〔m、n〕
In the formula (1-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, particularly preferably 1 or 2, and most preferably 1.
In the formula (1-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, particularly preferably 1 or 2, and most preferably 1.
〔Y 1 Bonded oxygen atom to W 1 Number of atoms between (chain length of connection)
In the formula (1-1), Y in the compound B 1 Bonded oxygen atom to W 1 The number of atoms (chain length of the bond) therebetween is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and still more preferably 2 to 10.
The compound B contains more than 2 and Y 1 When the bonded oxygen atom contains 2 or more W 1 In the case of (C) or containing more than 2Y 1 Bonded oxygen atoms and containing more than 2W 1 In the case of (1), Y 1 Bonded oxygen atom to W 1 The minimum number of atoms (chain length) among them may be within the above range.
In the present specification, "Y 1 Bonded oxygen atom to W 1 The term "number of atoms (chain length of connection)" means the chain length in which the 2 atoms or groups of atoms to be connected are connected to the shortest (minimum number of atoms) atom chain on the path connecting these atoms. For example, in the structure represented by the following formula, Y 1 Bonded oxygen atom to W 1 The number of atoms (chain length of the linkage) between the (methacryloyloxy groups) was 2.
[ chemical formula 37]
The molecular weight of the compound B is preferably 1,000 or less, preferably 100 to 900, more preferably 200 to 800.
[ Synthesis of Compound B ]
Compound B can be synthesized, for example, by the method described in examples below.
The method for synthesizing the compound B is not particularly limited, and other known methods may be used for synthesis.
Specific examples of the compound B include SA-1 to SA-25 used in examples, but are not limited thereto.
The content of the compound B is preferably 1 mass% or more relative to the total mass of the resin composition of the present invention. The content is more preferably 2% by mass or more, and still more preferably 3% by mass or more. The content is preferably 20% by mass or less, and more preferably 10% by mass or less.
The content of the compound B is preferably 1 to 40% by mass based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 3 mass% or more, still more preferably 5 mass% or more, and particularly preferably 6 mass% or more. The upper limit is more preferably 30 mass% or less, and still more preferably 20 mass% or less.
The compound B may be used alone or in combination of 2 or more. When 2 or more kinds are used in combination, the total amount thereof is preferably within the above range.
< other polymerizable Compound >
The resin composition of the present invention preferably further comprises a polymerizable compound (hereinafter, also referred to as "other polymerizable compound") different from the above-described compound B.
In particular, it is preferable that a compound (radical crosslinking agent, described later) different from the compound B is further contained as the radical polymerizable compound.
The other polymerizable compound is a compound having a polymerizable group and not belonging to the compound B.
The other polymerizable compound may be a radical crosslinking agent or other crosslinking agent, and preferably contains a radical crosslinking agent.
The content of the other polymerizable compound is preferably more than 0% by mass and 20% by mass or less relative to the total mass of the composition. The lower limit of the content is preferably 0.1 mass% or more, more preferably 1.0 mass% or more, and still more preferably 1.5 mass% or more. The upper limit of the content is preferably 15 mass% or less, more preferably 10 mass% or less.
The resin composition of the present invention may contain 1 kind of other polymerizable compound alone or 2 or more kinds. When it contains 2 or more, the sum of the amounts is preferably within the above range.
When the other polymerizable compound is contained, the content of the other polymerizable compound is preferably more than 0 part by mass and 200 parts by mass or less, more preferably 5 parts by mass to 100 parts by mass, and still more preferably 10 parts by mass to 50 parts by mass, relative to 100 parts by mass of the compound B.
[ free radical crosslinking agent ]
The resin composition of the present invention preferably contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
Among them, the group containing an ethylenically unsaturated bond is preferably a (meth) acryloyl group, (meth) acrylamide group or vinylphenyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
The radical crosslinking agent is preferably a compound having 1 or more ethylenically unsaturated bonds, more preferably a compound having 2 or more ethylenically unsaturated bonds. The radical crosslinking agent may have 3 or more ethylenically unsaturated bonds.
The compound having 2 or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 2 to 6 ethylenically unsaturated bonds.
Further, from the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably further comprises a compound having 2 ethylenically unsaturated bonds and a compound having 3 or more ethylenically unsaturated bonds.
The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, a sulfanyl group, or the like with a monofunctional or polyfunctional isocyanate or epoxy, a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, or the like can be preferably used. Further, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, thiols are preferable, and substitution reactants of unsaturated carboxylic acid esters or amides having releasable substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, thiols are more preferable. Further, as another example, a compound group substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like may be used instead of the unsaturated carboxylic acid. For a specific example, refer to the descriptions in paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, and these descriptions are incorporated herein.
The radical crosslinking agent is preferably a compound having a boiling point of 100℃or higher at 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 di (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tri (acryloxyethyl) isocyanurate, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then subjecting the resultant to (meth) acrylation, and epoxy acrylates or the like as the reaction product of an epoxy resin and (meth) acrylic acid, as described in each of Japanese patent publication Nos. 48-041708, 50-006034, 51-037193, 48-064183, 49-043191 and 52-030490; and mixtures of these. Furthermore, the compounds described in paragraphs 0254 to 0257 of JP-A2008-292970 are also preferred. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate, and the like can also be mentioned.
Further, as a preferable radical crosslinking agent other than the above, a compound having a fluorene ring and having 2 or more groups having an ethylenically unsaturated bond, and a cardo (cardo) resin described in japanese patent application laid-open publication No. 2010-160418, japanese patent application laid-open publication No. 2010-129825, japanese patent application laid-open publication No. 4364216, and the like can also be used.
Further, examples of the unsaturated compounds include specific unsaturated compounds described in Japanese patent publication No. 46-043946, japanese patent publication No. 01-040337 and Japanese patent publication No. 01-040336, and vinyl phosphonic acid compounds described in Japanese patent publication No. 02-025493. Furthermore, a perfluoroalkyl group-containing compound described in Japanese patent application laid-open No. 61-022048 can also be used. Furthermore, the compounds described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol.20, no.7,300 to 308 (1984) can also be used.
In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219, which are incorporated herein by reference, can be used.
Further, the compounds described in JP-A-10-062986 as the specific examples of the compounds represented by the formulas (1) and (2) can also be used as the radical crosslinking agent, and the compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resultant mixture.
Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein.
The radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available as KAYARAD-330 (Nippon Kayaku co., ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku co., ltd.)), a-TMMT (Shin-Nakamura Chemical co., ltd.)), dipentaerythritol penta (commercially available as KAYARAD D-310 (Nippon Kayaku co., ltd.)), dipentaerythritol hexa (commercially available as KAYARAD DPHA (Nippon Kayaku co., ltd.)), a-DPH (Shin-Nakamura chemical co., ltd.)), or a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. It is also possible to use these oligomer types.
As commercially available products of the radical crosslinking agent, for example, there may be mentioned 4-functional acrylate SR-494 having 4 ethyleneoxy chains manufactured by Sartomer Company, inc, 2-functional methacrylate Sartomer Company having 4 ethyleneoxy chains manufactured by Inc, SR-209, 231, 239, nippon Kayaku Co., ltd., 6-functional acrylate DPCA-60 having 6 ethyleneoxy chains manufactured by Inc., 3-functional acrylate TPA-330 having 3 isobutyleneoxy chains manufactured by Nippon Kayaku, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD. Co., ltd.), NK ESTER NK M-40G, NK ESTER 4G, ESTER M-9300, NK ESTER A-9300, UA-7200 (Shin-Nakamura Chemical Co., ltd.), DPHA-40H (manufactured by Nippon Kayaku, ltd.), UA-57306-306, UAB-140 (manufactured by UK.M.35 CO., LTD.), NK ESTER M-40G., ltd., UK.M.N. 6, UK. and UK.K. 3, or the like, which are manufactured by BLER-600, and the like.
As the radical crosslinking agent, urethane acrylates described in Japanese patent publication No. 48-041708, japanese patent application laid-open No. 51-037193, japanese patent application laid-open No. 02-032293, and Japanese patent application laid-open No. 02-016765, urethane compounds having an ethylene oxide skeleton described in Japanese patent publication No. 58-049860, japanese patent publication No. 56-017654, japanese patent publication No. 62-039417, and Japanese patent publication No. 62-039418 are also preferred. Further, as the radical crosslinking agent, a compound having an amino structure or a thioether structure in the molecule described in JP-A-63-277653, JP-A-63-260909 or JP-A-01-105238 can be used.
The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid group. Particularly preferred are the following compounds: in the radical crosslinking agent in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid group, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. Examples of the commercial products include TOAGOSEI CO., LTD. The polyacid-modified acrylic oligomers M-510 and M-520.
The radical crosslinking agent having an acid group preferably has an acid value of 0.1 to 300mgKOH/g, particularly preferably 1 to 100mgKOH/g. The acid value of the radical crosslinking agent is within the above range, and therefore, the production workability and further the developability are excellent. Furthermore, the polymerizability was good. The acid value was determined in accordance with JIS K0070: 1992, the measurement was performed.
From the viewpoints of resolution of the pattern and stretchability of the film, the resin composition preferably uses 2-functional methacrylate or acrylate.
Specific examples of the compound include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1, 6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol a EO (ethylene oxide) adduct diacrylate, bisphenol a EO adduct dimethacrylate, bisphenol a PO adduct diacrylate, bisphenol a PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid, E0 diacrylate, isocyanuric acid modified dimethacrylate, other 2-functional acrylates having urethane bonds, and 2-functional methacrylates having urethane bonds. These may be used in combination of 2 or more kinds as required.
For example, PEG200 diacrylate refers to a polyethylene glycol diacrylate having a formula weight of about 200 in polyethylene glycol chains.
From the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent. As the monofunctional radical crosslinking agent, there may be preferably used (meth) acrylic acid derivatives such as 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) acrylamide, epoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, and the like. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100 ℃ or higher at normal pressure is also preferable in order to suppress volatilization before exposure.
Examples of the radical crosslinking agent having a function of 2 or more include allyl compounds such as diallyl phthalate and triallyl trimellitate.
When the radical crosslinking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and still more preferably 30 mass% or less.
The radical crosslinking agent may be used alone or in combination of 1 or more than 2. When 2 or more kinds are used in combination, the total amount thereof is preferably within the above range.
[ other crosslinking Agents ]
The resin composition of the present invention preferably further comprises a crosslinking agent other than the radical crosslinking agent described above.
In the present invention, the other crosslinking agent is preferably a compound having a plurality of groups in the molecule which promote a reaction to form covalent bonds with other compounds in the composition or reaction products thereof by sensitization with the photoacid generator, photobase generator or the like, more preferably a compound having a plurality of groups in the molecule which promote a reaction to form covalent bonds with other compounds in the composition or reaction products thereof by the action of an acid or a base.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other crosslinking agent, a compound having at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group is preferable, and a compound having a structure in which at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferable.
Examples of the other crosslinking agent include compounds having the following structures: and a structure obtained by reacting an amino group-containing compound such as melamine, acetylene urea, alkylene urea, benzoguanamine, etc., with formaldehyde or formaldehyde and an alcohol to replace a hydrogen atom of the amino group with an acyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group. The method for producing these compounds is not particularly limited as long as they are compounds having the same structure as the compounds produced by the above method. The oligomer may be one in which methylol groups of these compounds are self-condensed with each other.
As the above amino group-containing compound, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using acetylene urea, urea or alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.
Among these, the resin composition of the present invention preferably contains at least 1 compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least 1 compound selected from acetylene urea-based crosslinking agents and melamine-based crosslinking agents described later.
Examples of the compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the urea structure described below, or a triazine.
The alkoxymethyl group or acyloxymethyl group contained in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the above compound is preferably 1500 or less, and preferably 180 to 1200.
[ chemical formula 38]
R 100 Represents an alkyl group or an acyl group.
R 101 R is R 102 Each independently represents a 1-valent organic group, and may be bonded to each other to form a ring.
Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula.
[ chemical formula 39]
Wherein X represents a single bond or a 2-valent organic group, each R 104 Each independently represents an alkyl group or an acyl group, R 103 Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group which is decomposed by the action of an acid to form an alkali-soluble group (e.g., a group which is detached by the action of an acid, a group which is formed by-C (R 4 ) 2 COOR 5 A group (R) 4 R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms 5 Represents groups which are detached by the action of an acid. )).
R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
Regarding the groups that are decomposed by the action of an acid to form alkali-soluble groups, the groups that are detached by the action of an acid are represented by-C (R 4 ) 2 COOR 5 R in the radicals represented 5 For example, there can be mentioned-C (R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 ) Etc.
Wherein R is 36 ～R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R is R 36 And R is R 37 Can be bonded to each other to form a ring.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
The alkyl group may be either a straight chain or a branched chain.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an alkyl group having 7 to 16 carbon atoms.
The aralkyl group refers to an aryl group substituted with an alkyl group, and the preferable modes of the alkyl group and the aryl group are the same as those of the alkyl group and the aryl group.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
Further, these groups may further have a known substituent within a range to obtain the effect of the present invention.
R 01 R is R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The group which is decomposed by the action of an acid to form an alkali-soluble group or the group which is detached by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group or the like. Further preferred is a tertiary alkyl ester group and an acetal group.
Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which an alkoxymethyl group of the following compound is changed to an acyloxymethyl group. Examples of the compound having an alkoxymethyl group or an acyloxymethyl group in the molecule include, but are not limited to, the following compounds.
[ chemical formula 40]
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The compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group may be commercially available or may be synthesized by a known method.
From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.
Specific examples of urea-based crosslinking agents include acetylene urea-based crosslinking agents such as monomethylolated acetylene urea, dimethylolated acetylene urea, trimethylolated acetylene urea, tetramethylolated acetylene urea, monomethylolated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetramethoxymethylated acetylene urea, monoethoxymethylacetylene urea, diethoxymethylacetylene urea, triethoxymethylacetylene urea, tetraethoxymethylated acetylene urea, monopropoxymethylacetylene urea, dipropoxymethylacetylene urea, tripropoxymethylacetylene urea, tetrapropoxymethylacetylene urea, monobutyloxymethylacetylene urea, dibutoxymethylated acetylene urea, tributoxymethylated acetylene urea or tetrabutoxymethylated acetylene urea;
Urea-based crosslinking agents such as dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea and dibutoxymethyl urea,
Vinyl urea cross-linking agents such as mono-methylolated vinyl urea or di-methylolated vinyl urea, mono-methoxymethylated vinyl urea, di-methoxymethylated vinyl urea, mono-ethoxymethylated vinyl urea, di-ethoxymethylated vinyl urea, mono-propoxymethylated vinyl urea, di-propoxymethylated vinyl urea, mono-or di-butoxymethylated vinyl urea,
Propylene urea-based crosslinking agents such as monocrystaline propylene urea, dimethylol propylene urea, monomethoxy methylated propylene urea, dimethoxy methylated propylene urea, monomethoxy methylated propylene urea, diethoxy methylated propylene urea, monopropoxy methylated propylene urea, dipropoxy methylated propylene urea, monobutyl oxymetylated propylene urea or dibutoxy methylated propylene urea,
1, 3-bis (methoxymethyl) -4, 5-dihydroxy-2-imidazolidinone, 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone, and the like.
Specific examples of the benzoguanamine-based crosslinking agent include monomethylol benzoguanamine, dimethylol benzoguanamine, trimethylol benzoguanamine, tetramethylol benzoguanamine, monomethylol methylated benzoguanamine, dimethoxymethyl benzoguanamine, trimethoxy methylated benzoguanamine, tetramethoxymethyl benzoguanamine, monoethoxymethyl benzoguanamine, diethoxymethyl benzoguanamine, triethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine, monopropoxymethyl benzoguanamine, dipropoxymethyl benzoguanamine, tripropoxymethyl benzoguanamine, tetrapropoxymethyl benzoguanamine, monobutyloxymethyl benzoguanamine, dibutoxymethyl benzoguanamine, tributoxymethyl benzoguanamine, tetrabutoxymethyl benzoguanamine, and tetrabutoxymethyl benzoguanamine.
As the compound having at least 1 group selected from the group consisting of hydroxymethyl and alkoxymethyl, a compound in which at least 1 group selected from the group consisting of hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) can be preferably used.
Specific examples of such compounds include xylylene glycol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethyl benzene hydroxymethyl benzoate, bis (hydroxymethyl) biphenyl, dimethyl bis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl benzene methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, 4',4 "-ethylenetris [2, 6-bis (methoxymethyl) phenol ], 5' - [2, 2-trifluoro-1- (trifluoromethyl) ethylene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ], 3', 5' -tetrakis (methoxymethyl) -1,1 '-biphenyl-4, 4' -diol, and the like.
As the other crosslinking agent, commercially available products can be used, and as a preferred commercially available product, examples thereof include 46DMOC, 46DMOEP (manufactured by ASAHIYUKIZAICORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34-X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisc-P, DMOM-PC DMOM-PTBP, DMOM-MBPC, triML-P, triML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., above, LTD), NIKALAC (registered trademark, the same as described below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (SANWA CHEMICAL co., LTD) and the like.
Further, the resin composition of the present invention preferably further contains at least 1 compound selected from the group consisting of an epoxy compound, an oxetane compound and a benzoxazine compound as another crosslinking agent.
Epoxy compound (epoxy group-containing compound)
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 less and does not cause dehydration reaction due to crosslinking, and thus film shrinkage is less likely to occur. Therefore, by containing the epoxy compound, the low-temperature curing and warpage of the resin composition of the present invention can be effectively suppressed.
The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, and the number of repeating units is preferably 2 to 15.
Examples of the epoxy compound include bisphenol a epoxy resins; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like, or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethylsiloxane (glycidoxypropyl) and the like, but are not limited thereto. Specifically, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON-665-EXP-S, EPICLON (registered trademark) N-740 (the above are trade names, DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, new Japan Chemical Co., ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, ADEKA CORPORATION, CELLOXDE 2021P, CELLOXIDE (registered trademark) 2081, CELLOXDE 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (trade name, daicel Corporation, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade name, nippon Kayaku Co., ltd.) and the like. Furthermore, the following compounds may also be preferably used.
[ chemical formula 42]
Wherein n is an integer of 1 to 5, and m is an integer of 1 to 20.
In the above structure, n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of both heat resistance and improvement of elongation.
Oxetane compounds (compounds having an oxetanyl group)
Examples of oxetane compounds include compounds having 2 or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexyl methyl) oxetane, and 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester. Specifically, TOAGOSEI CO. LTD. ARON OXETANE series (for example, OXT-121, OXT-221) may be preferably used, and these may be used alone or 2 or more may be mixed.
Benzoxazine compound (compound having benzoxazolyl group)
The benzoxazine compound is preferable because it does not outgas during curing due to a crosslinking reaction caused by a ring-opening addition reaction, and further reduces heat shrinkage to suppress warpage.
Preferable examples of the benzoxazine compound include P-d type benzoxazine, F-a type benzoxazine (trade name, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used alone, or 2 or more kinds may be mixed.
The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The other crosslinking agent may be contained only in 1 kind, or may be contained in 2 or more kinds. When the amount of the other thermal crosslinking agent is 2 or more, the total amount is preferably within the above range.
[ polymerization initiator ]
The resin composition of the present invention preferably contains a polymerization initiator, preferably contains a radical polymerization initiator. The radical polymerization initiator preferably includes a radical polymerization initiator capable of initiating polymerization by light and/or heat. Particularly preferably, the photo radical polymerization initiator is contained.
The photo radical polymerization initiator is not particularly limited, and may be appropriately selected from known photo radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays ranging from the ultraviolet region to the visible region is preferable. Moreover, it may be an active agent that exerts some action with the photosensitizing agent that is excited by light and generates active radicals.
The photo radical polymerization initiator preferably contains at least 1 initiator having a molecular weight of at least about 50 L.mol in a wavelength range of about 240 to 800nm (preferably 330 to 500 nm) -1 ·cm -1 A compound having a molar absorptivity. The molar absorptivity of the compound can be measured by a known method. For example, it is preferable to measure the content of the organic compound at a concentration of 0.01g/L by using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co.) using an ethyl acetate solvent.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole, oxime derivatives, and the like, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α -amino ketone compounds such as aminoacetophenone, α -hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference is made to paragraphs 0165 to 0182 of Japanese unexamined patent publication (Kokai) No. 2016-027357 and paragraphs 0138 to 0151 of International publication (Kokai) No. 2015/199219, which are incorporated herein by reference. Examples of the initiator include a compound described in JP-A-2014-130173 at the stage 0065-0111, JP-A-6301489, MATERIAL STAGE-60 p, vol.19, no.3, 2019, a peroxide-based photopolymerization initiator described in International publication No. 2018/221177, a photopolymerization initiator described in International publication No. 2018/110179, a photopolymerization initiator described in JP-A-2019-043864, a photopolymerization initiator described in JP-A-2019-044030, and a peroxide-based initiator described in JP-A-2019-167313, which are incorporated herein by reference.
Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, incorporated herein by reference. Among the commercial products, KAYACURE DETX-S (Nippon Kayaku co., ltd.) may also be preferably used.
In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine oxide initiator described in JP-A-4225898 can be used, and these are incorporated herein.
As the alpha-hydroxyketone initiator, omnirad 184, omnirad 1173, omnirad 2959, omnirad 127 (manufactured by IGM Resins B.V. above), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (manufactured by BASF corporation) can be used.
As the α -aminoketone initiator, omnirad 907, omnirad 369E, omnirad 379EG (manufactured by IGM Resins B.V. above), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF corporation) can be used.
As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179, which matches the maximum absorption wavelength to a light source having a wavelength of 365nm or 405nm, etc., can be used, and these contents are incorporated in the present specification.
Examples of the acylphosphine oxide initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. As the catalyst, omnirad 819, omnirad TPO (manufactured by IGM Resins B.V. above), IRGACURE-819, IRGACURE-TPO (trade name: manufactured by BASF corporation) can be used.
Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF corporation), keycure VIS813 (King Brother Chem Co., ltd.).
As the photo radical polymerization initiator, an oxime compound is more preferably exemplified. By using an oxime compound, the exposure latitude can be further 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 a compound described in Japanese patent application laid-open No. 2001-233846, a compound described in Japanese patent application laid-open No. 2000-080068, a compound described in Japanese patent application laid-open No. 2006-342166, a compound described in J.C.S.Perkin II (1979, pages 1653-1660), a compound described in J.C.S.Perkin II (1979, pages 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pages 202-232), a compound described in Japanese patent application laid-open No. 2000-066385, a compound described in Japanese patent application laid-open No. 2004-534797, a compound described in Japanese patent application laid-open No. 6065596, a compound described in International publication No. 2015/152153, a compound described in International publication No. 2017/051680, a compound described in Japanese patent application laid-open No. 2017-003865, a compound described in International publication No. 2015-1675, a compound described in International publication No. 2015-2015, a compound described in International publication No. 2015, and the publication No. 2015-2015.
Preferable oxime compounds include, for example, 3- (benzoyloxy (imino)) butan-2-one, 3- (acetoxy (imino)) butan-2-one, 3- (propionyloxy (imino)) butan-2-one, 2- (acetoxy (imino)) pentan-3-one, 2- (acetoxy (imino)) -1-phenylpropan-1-one, 2- (benzoyloxy (imino)) -1-phenylpropan-1-one, 3- ((4-toluenesulfonyloxy) (imino)) butan-2-one, and 2- (ethoxycarbonyloxy (imino)) -1-phenylpropan-1-one of the following structures. In the resin composition of the present invention, an oxime compound (oxime-based photo radical polymerization initiator) is preferably used as a photo radical polymerization initiator, in particular. The oxime-based photo-radical polymerization initiator has a linking group > c=n-O-C (=o) -, in the molecule.
[ chemical formula 43]
Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF corporation as described above), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION), and photo radical polymerization initiator 2 described in Japanese patent application laid-open No. 2012-014052 may be preferably used. In addition, TR-PBG-304, TR-PBG-305 (Changzhou Tronly New Electronic Material s CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (ADEKA CORPORATION). Further, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, an oxime compound having the following structure can also be used.
[ chemical formula 44]
As the photo radical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include a compound described in japanese patent application laid-open No. 2014-137466 and a compound described in japanese patent No. 06636081, which are incorporated herein by reference.
As the photo radical polymerization initiator, an oxime compound having at least 1 benzene ring of carbazole ring as a skeleton of naphthalene ring can also be used. Specific examples of such oxime compounds include those described in international publication No. 2013/083505, which are incorporated herein by reference.
Oxime compounds having a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-26261028A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852A, and compound (C-3) described in paragraph 0101 of JP 2013-164471A, which are incorporated in the present specification.
As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably provided as a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, and 0007 to 0025 of Japanese patent application laid-open No. 4223071, which are incorporated herein by reference. Further, as the oxime compound having a nitro group, ADEKA ARKLS NCI-831 (ADEKA CORPORATION).
As the photo radical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 described in International publication No. 2015/036910.
As the photo radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International publication No. 2019/088055, which are incorporated herein by reference.
As the photopolymerization initiator, an aromatic ring group Ar having an electron withdrawing group introduced into an aromatic ring can also be used OX1 Is also referred to as oxime compound OX below. Ar as the above aromatic ring group OX1 Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, preferably an acyl group and a nitro group, more preferably an acyl group, and further preferably a benzoyl group, from the viewpoint of facilitating formation of a film excellent in light resistance. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkenyl group, alkylthio group, arylthio group, acyl group or amino group, more preferably an alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group or amino group, still more preferably an alkoxy group, alkylthio group or amino group.
The oxime compound OX is preferably at least 1 selected from the group consisting of a compound represented by the formula (OX 1) and a compound represented by the formula (OX 2), more preferably a compound represented by the formula (OX 2).
[ chemical formula 45]
Wherein R is X1 Represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphono, carbamoyl or sulfamoyl,
R X2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy or amino,
R X3 ～R X14 each independently represents a hydrogen atom or a substituent.
Wherein R is X10 ～R X14 At least 1 of which is an electron withdrawing group.
In the above formula, R is preferably X12 R is an electron withdrawing group X10 、R X11 、R X13 、R X14 Is a hydrogen atom.
Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of japanese patent No. 4600600, which are incorporated herein by reference.
Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in japanese patent application laid-open No. 2007-269779, an oxime compound having a thioaryl group shown in japanese patent application laid-open No. 2009-191061, and the like, which are incorporated herein by reference.
From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethyl 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, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, 3-aryl-substituted coumarin compounds.
More preferred photo radical polymerization initiator is trihalomethyltriazine compound, α -amino ketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzophenone compound, acetophenone compound, still more preferred is at least 1 compound selected from trihalomethyltriazine compound, α -amino ketone compound, metallocene compound, oxime compound, triarylimidazole dimer, benzophenone compound, still more preferred is metallocene compound or oxime compound.
The photo radical polymerization initiator may be a benzophenone, an aromatic ketone such as N, N ' -tetramethyl-4, 4' -diaminobenzophenone (michler's ketone), an aromatic ketone such as N, N ' -tetraalkyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinophenone-1, a benzoin ether compound such as alkylanthraquinone, a benzoin ether compound such as benzoin alkyl ether, a benzoin compound such as benzoin, alkylbenzoin, a benzyl derivative such as benzyl dimethyl ketal, or the like. Furthermore, a compound represented by the following formula (I) can also be used.
[ chemical formula 46]
In the formula (I), R I00 Is 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, or 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, or a carbon atomAt least 1 substituted phenyl or biphenyl group in alkyl group with 1-4 sub-numbers, R I01 Is a group represented by formula (II) or is associated with R I00 The same radicals R I02 ～R I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.
[ chemical formula 47]
Wherein R is I05 ～R I07 R is the same as the R of the formula (I) I02 ～R I04 The same applies.
The photo radical polymerization initiator may be any one of those described in paragraphs 0048 to 0055 of International publication No. 2015/125469, incorporated herein by reference.
As the photo radical polymerization initiator, a 2-functional or 3-functional or more photo radical polymerization initiator can be used. By using such a photo radical polymerization initiator, 2 or more radicals are generated from one molecule of the photo radical polymerization initiator, and thus good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced, solubility in a solvent or the like is increased, and precipitation is less likely to occur with the passage of time, whereby the stability of the resin composition with time can be improved. Specific examples of the 2-functional or 3-functional or more photo-radical polymerization initiator include the photoinitiators of oxime esters described in JP-A2010-527339, JP-A2011-524436, international publication No. 2015/004565, the dimers of oxime compounds described in JP-A0407-0412, international publication No. 2017/033680 and 0039-0055, the compounds (E) and (G) described in JP-A2013-522445, cmpd 1-7 described in International publication No. 2016/034963, oxime ester photoinitiators described in JP-A2017-523465 and 0007, photoinitiators of JP-A0020-0033, photoinitiators of JP-A2017-151342 and oxime ester photoinitiators of JP-A0017-0026 and JP-A6469669, etc., which are described in the specification.
When the photo radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition of the present invention. The photopolymerization initiator may be contained in an amount of 1 or 2 or more. When the photopolymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.
In addition, the photopolymerization initiator may also function as a thermal polymerization initiator, and thus crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
[ sensitizer ]
The resin composition may contain a sensitizer. The sensitizer absorbs a specific active radiation to be in an electron-excited state. The sensitizer in an electron excited state is brought into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator or the like to cause an electron transfer, an energy transfer, heat generation or the like. Thus, the thermal radical polymerization initiator and the photo radical polymerization initiator cause chemical changes to decompose and generate radicals, acids or bases.
As the sensitizer that can be used, compounds such as benzophenone-based, milone-based, coumarin-based, pyrazole azo-based, aniline azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based and the like can be used.
As the sensitizer, for example, examples thereof include midone, 4' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 4' -bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenyl biphenyl) -benzothiazole, 2- (p-dimethylaminophenyl vinylidene) benzothiazole, and 2- (p-dimethylaminophenylvinylene) isonaphthylthiazole, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone, 3' -carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7- (diethylamino) coumarin-3-carboxylic acid ethyl ester), and, N-phenyl-N ' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyrene) benzoxazole, 2- (p-dimethylaminostyrene) benzothiazole, 2- (p-dimethylaminostyrene) naphthalene (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4' -dimethylacetanilide, and the like.
Furthermore, other sensitizing colorants can be used.
For details of the sensitizing dye, reference is made to paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which are incorporated herein by reference.
When the resin composition 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 even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of 2 or more.
[ chain transfer agent ]
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in pages 683-684 of the third edition of the Polymer dictionary (university of Polymer (The Society of Polymer Science, japan) eds., 2005). As the chain transfer agent, for example, a chain transfer agent having-S-, -SO within the molecule can be used 2 The group of compounds S-, -N-O-, SH, PH, siH and GeH, dithiobenzoate esters having thiocarbonylthio groups for RAFT (Reversible Addition Fragmentation chain Transfer: reversible addition fragmentation chain transfer) polymerization, trithiocarbonates, dithiocarbamates, xanthate compounds, etc. These supply hydrogen to the low activity radicals to generate radicals, or may generate radicals by deprotonation after oxidation. In particular, a thiol compound can be preferably used.
The chain transfer agent may be a compound described in paragraphs 0152 to 0153 of International publication No. 2015/199219, incorporated herein by reference.
When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be 1 or 2 or more. When the chain transfer agent is 2 or more, the total amount thereof is preferably within the above range.
< alkali Generator >
The resin composition of the present invention may contain a base generator. Here, the base generator means a compound capable of generating a base by physical action or chemical action. The alkali generator preferable for the resin composition of the present invention includes a thermal alkali generator and a photobase generator.
In particular, when the resin composition contains a precursor of the cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor is accelerated by heating, and the cured product has good mechanical properties and chemical resistance, for example, the interlayer insulating film for a rewiring layer contained in a semiconductor package has good performance.
The alkali generator may be an ionic alkali generator or a nonionic alkali generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The alkali generator of the present invention is not particularly limited, and a known alkali generator can be used. As the known base generating agent, for example, a carbamoyl oxime compound, a carbamoyl hydroxylamine compound, a carbamic acid compound, a carboxamide compound, an acetamide compound, a carbamic acid ester compound, a benzyl carbamic acid ester compound, a nitrobenzyl carbamic acid ester compound, a sulfonamide compound, an imidazole derivative compound, an amine imide compound, a pyridine derivative compound, an α -aminoacetophenone derivative compound, a quaternary ammonium salt derivative compound, a pyridinium salt, an α -lactone ring derivative compound, an amine imide compound, a phthalimide derivative compound, an acyloxyimide compound, or the like can be used.
Specific examples of the nonionic base generator include compounds represented by the formula (B1), the formula (B2), and the formula (B3).
[ chemical formula 48]
Rb in the formulae (B1) and (B2) 1 、Rb 2 Rb 3 Each independently is an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. Wherein Rb 1 Rb 2 And not simultaneously become hydrogen atoms. Furthermore, rb 1 、Rb 2 Rb 3 None of them has a carboxyl group. In the present specification, the tertiary amine structure means a structure in which all of 3 bonds of a 3-valent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, the present invention is not limited to this case, and the carbon atom to be bonded is a carbon atom forming a carbonyl group, that is, an amide group is formed together with a nitrogen atom.
In the formulae (B1) and (B2), rb is preferably 1 、Rb 2 Rb 3 At least 1 of which comprises a cyclic structure, more preferably at least 2 of which comprises a cyclic structure. The cyclic structure may be any of a single ring and a condensed ring, and a condensed ring formed by condensing a single ring or 2 single rings is preferable. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.
More specifically, rb 1 Rb 2 Preferably, the compound is a hydrogen atom, an alkyl group (having a carbon number of preferably 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), an alkenyl group (having a carbon number of preferably 2 to 24, more preferably 2 to 18, still more preferably 3 to 12), an aryl group (having a carbon number of preferably 6 to 22, more preferably 6 to 18, still more preferably 6 to 10), or an aralkyl group (having a carbon number of preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 12). These groups may have substituents within a range that exerts the effects of the present invention. Rb (Rb) 1 With Rb 2 Can be bonded to each other to form a ring. As the ring formed, a 4-to 7-membered nitrogen-containing heterocycle is preferable. Rb (Rb) 1 Rb 2 In particular, a linear, branched or cyclic alkyl group which may have a substituent (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), a cycloalkyl group which may have a substituent (the number of carbon atoms is preferably 3 to 24, more preferably 3 to 18, still more preferably 3 to 12), and a cyclohexyl group which may have a substituent are preferable.
As Rb 3 Examples thereof include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), an aralkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxy group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms) or an aralkoxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12). Among them, cycloalkyl groups (having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), aralkenyl groups, and aralkoxy groups are preferable. Rb (Rb) 3 Further, the substituent may be present within a range that exerts the effects of the present invention.
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 49]
In the formula, rb 11 Rb 12 And Rb 31 Rb 32 Respectively with Rb in formula (B1) 1 Rb 2 The meaning is the same.
Rb 12 The alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), the alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms) may have a substituent in a range that exerts the effect of the present invention. Wherein Rb 13 Aralkyl groups are preferred.
Rb 33 Rb 34 Each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), or a hydrogen atom.
Rb 35 The alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), the alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and preferably the aryl group.
The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1 a).
[ chemical formula 50]
Rb 11 Rb 12 And Rb in formula (B1-1) 11 Rb 12 The meaning is the same.
Rb 15 Rb 16 The examples of the "alkyl" are preferably a hydrogen atom, an alkyl group (having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an aralkyl group (having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms), and a hydrogen atom or a methyl group.
Rb 17 The aromatic group is preferably an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), or the like.
[ chemical formula 51]
In the formula (B3), L is a 2-valent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain linking the adjacent oxygen atoms and carbon atoms, and represents a hydrocarbon group having 3 or more atoms on the path of the linking chain. And R is N1 R is R N2 Each independently represents a 1-valent organic group.
In the present specification, the term "link chain" refers to a chain in which the connection objects are connected at the shortest (minimum atomic number) distance among atomic chains on a path connecting 2 atoms or groups of atoms of the connection objects. For example, in a compound represented by the following formula, L is composed of styrene and has a vinyl group as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4.
[ chemical formula 52]
The number of carbon atoms in L of the formula (B3) (including carbon atoms other than the carbon atoms in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. The upper limit of the chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of rapidly proceeding the intramolecular cyclization reaction. In particular, the chain length of the linkage of L is preferably 4 or 5, and most preferably 4. Specific examples of preferred compounds for the base generator include, for example, compounds described in paragraphs 0102 to 0168 of International publication No. 2020/066416 and compounds described in paragraphs 0143 to 0177 of International publication No. 2018/038002.
The base generator preferably further comprises a compound represented by the following formula (N1).
[ chemical formula 53]
In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group, R C1 Represents a hydrogen atom or a protecting group, and L represents a 2-valent linking group.
L is a 2-valent linking group, preferably a 2-valent organic group. The chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between 2 carbonyl groups in the formula.
In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), preferably a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), preferably an aliphatic hydrocarbon group. As R N1 R is R N2 If an aliphatic hydrocarbon group is used, the alkali generated is preferably highly basic. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in an aliphatic hydrocarbon chain, an aromatic ring, or a substituent. In particular, the manner in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.
As a constituent R N1 R is R N2 Examples of the aliphatic hydrocarbon group(s) include a linear or branched alkyl group, a cyclic alkyl group, a group related to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The number of carbon atoms of the linear or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and still more preferably 3 to 12. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and the like.
The number of carbon atoms of the cyclic alkyl group is preferably 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.
The number of carbon atoms of the group involved in the combination of the chain alkyl group and the cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and still more preferably 4 to 12. Examples of the group involved in the combination of the chain alkyl group and the cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, ethylcyclohexylethyl group, and the like.
The number of carbon atoms of the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched.
Wherein R is from the viewpoint of increasing the boiling point of a base formed by decomposition to be described later N1 R is R N2 Preferably an alkyl group having 5 to 12 carbon atoms. Among them, in the formulation in which adhesion to the metal (e.g., copper) layer is important, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
R N1 R is R N2 Can be connected with each other to form a ring structure. When the cyclic structure is formed, an oxygen atom or the like may be present in the chain. And R is N1 R is R N2 The cyclic structure may be a single ring or a condensed ring, and is preferably a single ring. The cyclic structure to be formed is preferably a 5-or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring, and examples thereof include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
R C1 Represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and the protecting group which is decomposed by an acid is preferably exemplified.
Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include methyl, ethyl, isopropyl, t-butyl, and cyclohexyl. The chain alkyl group having an oxygen atom in the chain includes, specifically, an alkoxyalkyl group, and more specifically, a methoxymethyl group (MOM), an ethoxyethyl group (EE), and the like. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, an epoxypropyl group, an oxetanyl group, a tetrahydrofuranyl group, and a Tetrahydropyran (THP) group.
The 2-valent linking group constituting L is not particularly limited, and is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have a kind of atom other than a carbon atom in the hydrocarbon chain. More specifically, a 2-valent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a 2-valent aromatic hydrocarbon group, or a group related to a combination of a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a 2-valent aromatic hydrocarbon group is more preferable, and a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. These groups preferably do not have an oxygen atom.
The number of carbon atoms of the 2-valent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and still more preferably 2 to 6. The number of carbon atoms of the 2-valent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the 2-valent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10. The number of carbon atoms of the group (for example, an arylene alkyl group) involved in the combination of the 2-valent aliphatic hydrocarbon group and the 2-valent aromatic hydrocarbon group is preferably 7 to 22, more preferably 7 to 18, and still more preferably 7 to 10.
The linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.
The number of carbon atoms of the linear or branched chain alkylene group is preferably 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4.
The number of carbon atoms of the cyclic alkylene group is preferably 3 to 12, more preferably 3 to 6.
The number of carbon atoms of the group involved in the combination of the chain alkylene group and the cyclic alkylene group is preferably 4 to 24, more preferably 4 to 12, and still more preferably 4 to 6.
The alkylene group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched. The number of carbon atoms of the alkylene group having an oxygen atom in the chain is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3.
The number of carbon atoms of the linear or branched alkenyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 3. The number of c=c bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
The number of carbon atoms of the cyclic alkenylene group is preferably 3 to 12, more preferably 3 to 6. The number of c=c bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.
The number of carbon atoms of the arylene group is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10.
The number of carbon atoms of the arylene alkylene is preferably 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11.
Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, and arylene alkylene groups, and more preferred are 1, 2-vinyl groups, propane diyl groups (particularly 1, 3-propane diyl groups), cyclohexane diyl groups (particularly 1, 2-cyclohexane diyl groups), vinylidene groups (particularly cis-vinylidene groups), phenylene groups (1, 2-phenylene groups), phenylene methylene groups (particularly 1, 2-phenylene methylene groups), and ethyleneoxy vinyl groups (particularly 1, 2-ethyleneoxy-1, 2-vinyl groups).
The following examples are given as examples of the alkali generator, but the present invention should not be construed as being limited thereto.
[ chemical formula 54]
The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.
Specific examples of preferred compounds for the ionic base generator include compounds described in paragraphs 0148 to 0163 of International publication No. 2018/038002.
Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.
[ chemical formula 55]
Specific examples of the imide salt include the following compounds, but the present invention is not limited thereto.
[ chemical formula 56]
When the resin composition of the present invention contains the alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
The alkali generator can be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably within the above range.
< solvent >
The resin 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 esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, alcohols, and the like.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, ethyl 2-alkoxy-2-methyl propionate, and ethyl 2-alkoxypropionate, etc.), methyl 2-alkoxypropionate, methyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate, etc. (e.g., methyl 2-ethoxypropionate, etc.), ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl caproate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like.
As the ethers, for example, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, and the like can be preferably used.
Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, l-glucosone (levoglucosenone), and dihydro-l-glucosone.
Examples of the cyclic hydrocarbon include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
As the sulfoxide, dimethyl sulfoxide is preferable, for example.
As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like can be preferably used.
Preferred examples of the urea include N, N, N ', N' -tetramethylurea and 1, 3-dimethyl-2-imidazolidinone.
Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
The solvent is preferably mixed with 2 or more solvents from the viewpoint of improvement of the properties of the coated surface.
In the present invention, it is preferable that the solvent be 1 or a mixed solvent of 2 or more solvents selected from 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 acetate, levoglucosone, and dihydro-levoglucosone. Particularly preferred are dimethyl sulfoxide and gamma-butyrolactone in combination or N-methyl-2-pyrrolidone and ethyl lactate in combination.
The solvent content is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, still more preferably 10 to 70% by mass, and still more preferably 20 to 70% by mass of the total solid content concentration of the resin composition of the present invention from the viewpoint of coatability. The solvent content is adjusted according to the thickness required by the coating film and the coating method.
The resin composition of the present invention may contain only 1 solvent, or may contain 2 or more solvents. When the solvent is contained in an amount of 2 or more, the total amount thereof is preferably within the above range.
< Metal adhesion improver >
The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improver include a silane coupling agent having an alkoxy silicon group, an aluminum-based adhesion promoter, a titanium-based adhesion promoter, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β -keto ester compound, an amino compound, and the like.
[ silane coupling agent ]
Examples of the silane coupling agent include a compound described in paragraph 0167 of Japanese patent application laid-open 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 patent application laid-open 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. 2014/097594, a compound described in paragraphs 2017 to 0078 of Japanese patent application laid-open No. 2018-173573, and the like. Further, as described in paragraphs 0050 to 0058 of JP 2011-128358, it is also preferable to use 2 or more different silane coupling agents. Furthermore, the following compounds are also preferably used as the silane coupling agent. In the following formula, me represents methyl group, and Et represents ethyl group.
[ chemical formula 57]
Examples of the other silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidenepropylamine, N-phenyl-3-aminopropyltrimethoxysilane, trimethoxysilyl, 3-methoxypropyl isocyanurate, 3-methoxypropylpropyltrimethoxysilane, 3-mercaptopropyl silane, mercapto-3-ethoxypropyl silane, mercapto-3-propyl-methoxypropyl silane, mercapto-3-propyl-3-propylmercapto-propyl-silane, and the like, 3-trimethoxysilylpropyl succinic anhydride. These can be used singly or in combination of 1 or more than 2.
[ aluminum series adhesive auxiliary agent ]
Examples of the aluminum-based adhesive auxiliary agent include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum ethylacetoacetate diisopropyl ester, and the like.
Further, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A2014-186186 and thioether compounds described in paragraphs 0032 to 0043 of JP-A2013-072935 can be used, and these are incorporated herein.
The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the lower limit value is not less than the upper limit value, the adhesion between the pattern and the metal layer is improved, and when the upper limit value is not more than the upper limit value, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be 1 or 2 or more. When 2 or more kinds are used, the total thereof is preferably within the above range.
< migration inhibitor >
The resin composition of the present invention preferably further comprises a migration inhibitor. By including the migration inhibitor, transfer of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.
The migration inhibitor is not particularly limited, and 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-pyran ring, 6H-pyran ring, triazine ring), thiourea compounds, compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2, 4-triazole, benzotriazole, 3-amino-1, 2, 4-triazole, and 3, 5-diamino-1, 2, 4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.
Alternatively, an ion scavenger that traps anions such as halide ions can be used.
As other migration inhibitors, rust inhibitors described in paragraph 0094 of japanese patent application laid-open publication No. 2013-015701, compounds described in paragraphs 0073-0076 of japanese patent application laid-open publication No. 2009-283711, compounds described in paragraph 0052 of japanese patent application laid-open publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of japanese patent application laid-open publication No. 2012-194520, compounds described in paragraph 0166 of international publication No. 2015/199219, and the like can be used, and these are incorporated into the present specification.
Specific examples of migration inhibitors include the following compounds.
[ chemical formula 58]
When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass% relative to the total solid content of the resin composition of the present invention.
The migration inhibitor may be 1 or 2 or more. When the migration inhibitor is 2 or more, the total thereof is preferably within the above range.
< polymerization inhibitor >
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.
As specific compounds of the polymerization inhibitor, p-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol (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-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthalene) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-t-butyl-4-methylphenol, 5-nitroso-5-hydroxy-3, 3-hydroxy-benzyl-4, 3H-tri-4, 3H-hydroxybenzyl ketone, 3, 5H-tri-4-hydroxy-3H-3, 5-t-butyl-4-hydroxy-methyl-4, 2, 6-tetramethylpiperidine 1-oxyl, 2, 6-tetramethylpiperidine 1-oxyl, phenothiazine, phenazine, 1-diphenyl-2-picrylhydrazine, copper (II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like. Further, a polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and a compound described in paragraphs 0031 to 0046 of International publication No. 2015/125469, which are incorporated herein by reference, can also be used.
When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.
The polymerization inhibitor may be 1 or 2 or more. When the polymerization inhibitor is 2 or more, the total amount thereof is preferably within the above range.
< other additives >
The resin composition of the present invention can be blended with various additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anticoagulants, phenolic compounds, other high molecular compounds, plasticizers, other assistants (e.g., defoamers, flame retardants, etc.) and the like as necessary within the range to obtain the effects of the present invention. By properly containing these components, properties such as film physical properties can be adjusted. For these components, for example, reference can be made to the descriptions of paragraphs 0183 and later of Japanese patent application laid-open No. 2012-003225 (paragraph 0237 of the specification of corresponding U.S. patent application publication No. 2013/0034812), and the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of Japanese patent application laid-open No. 2008-250074, and the like, which are incorporated herein by reference. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
[ surfactant ]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
By adding the surfactant to the resin composition of the present invention, the liquid properties (particularly fluidity) when the resin composition is prepared into a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, when a film is formed using a coating liquid to which a surfactant-containing composition is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, thereby improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, a film having a uniform thickness with less thickness unevenness can be formed more favorably.
Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAPACE F144, MEGAPACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC Corporation above), fluoro FC430, fluoro FC431, fluoro FC171, novec FC4430, novec FC4432 (manufactured by 3M Japan Limited above), surflon S-382, surflon SC-101, surflon SC-103, surflon SC-104, surflon SC-105, surflon SC1068, surflon SC-381, surflon SC-383, surflon S393, surfKH-40 (manufactured by LTCO above), liquid FC 636, PF 36, PF 20, and the other types of PF 20. The fluorine-based surfactant may be any of the compounds described in paragraphs 0015 to 0158 of Japanese patent application laid-open No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese patent application laid-open No. 2011-132503, which are incorporated herein by reference. As the fluorine-based surfactant, a block polymer can be used, and specific examples thereof include compounds described in japanese patent application laid-open publication No. 2011-89090, which are incorporated herein.
The fluorine-containing polymer compound (including a repeating unit derived from a (meth) acrylate compound having a fluorine atom and a repeating unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group)) can also be preferably used as the fluorine-containing surfactant used in the present invention.
[ chemical formula 59]
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A2010-164965, which are incorporated herein by reference. Examples of commercial products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective in uniformity of thickness of the coating film and liquid saving property, and has good solubility in the composition.
Examples of silicone surfactants include Toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by ltd. Above) and other silicone surfactants such as Dow Corning Toray co., ltd. Above), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials inc. Above), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical co., ltd. Above), BYK307, BYK323, BYK330 (manufactured by BYK Chemie GmbH above), and the like.
Examples of hydrocarbon surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T (TAKEMOTO OIL & FAT CO, LTD).
Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, and the like), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Examples of the commercial products include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF corporation), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF corporation), solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO., manufactured by LTD), OLFIN E1010, surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., ltd.), and the like.
Specific examples of the cationic surfactant include organosiloxane polymer KP341 (Shin-Etsu Chemical co., ltd., (meth) acrylic (co) polymer poly flow nos. 75, 77, 90, 95 (Kyoeisha Chemical co., ltd.,) and W001 (Yusho co., ltd.)) and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (Yusho co., ltd.), and saldet BL (manufactured by SANYO KASEI co.ltd.).
The surfactant may be used in an amount of 1 or 2 or more.
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.
[ higher fatty acid derivative ]
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention so as to be biased to the surface of the resin composition of the present invention during drying after coating.
The higher fatty acid derivative may be a compound described in paragraph 0155 of International publication No. 2015/199219, which is incorporated herein by reference.
When the resin 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 relative to the total solid content of the resin composition of the present invention. The number of the higher fatty acid derivatives may be 1 or 2 or more. When the number of higher fatty acid derivatives is 2 or more, the total thereof is preferably within the above range.
[ thermal polymerization initiator ]
The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a compound having polymerizability. The addition of the thermal radical polymerization initiator can further cause the polymerization reaction of the resin and the polymerizable compound, and thus can further improve the solvent resistance. The photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063254, which are incorporated herein by reference.
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 even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. The thermal polymerization initiator may be contained in an amount of 1 or 2 or more. When the thermal polymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.
[ inorganic particles ]
The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.
The average particle diameter of the inorganic particles is preferably 0.01 to 2.0. Mu.m, more preferably 0.02 to 1.5. Mu.m, still more preferably 0.03 to 1.0. Mu.m, particularly preferably 0.04 to 0.5. Mu.m.
The average particle diameter of the inorganic particles is a primary particle diameter and is a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (NIKKISO co., ltd.).
When the above measurement is difficult, the measurement can be performed by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.
[ ultraviolet absorber ]
The compositions of the present invention may comprise an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.
Examples of the salicylate-based ultraviolet light absorber include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate, and examples of the benzophenone-based ultraviolet light absorber include 2,2' -dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber include 2- (2 '-hydroxy-3', 5 '-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-t-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -t-amyl-5 '-isobutylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-isobutyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -isobutyl-5 '-propylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-t-butylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, and 2- [2 '-hydroxy-5' - (1, 3-tetramethyl) phenyl ] benzotriazole.
Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3, 3-diphenylacrylate and 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate. Further, examples of the triazine-based ultraviolet light absorber include mono (hydroxyphenyl) triazine compounds such as 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, and 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; bis (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-propoxyphenyl) -6- (4-methylphenyl) -1,3, 5-triazine, and 2, 4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine; tris (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, and 2,4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1,3, 5-triazine.
In the present invention, 1 kind of the above-mentioned various ultraviolet absorbers may be used alone, or 2 or more kinds may be used in combination.
The composition of the present invention may or may not contain an ultraviolet absorber, but when contained, the content of the ultraviolet absorber is preferably 0.001 mass% or more and 1 mass% or less, more preferably 0.01 mass% or more and 0.1 mass% or less, relative to the total solid content mass of the composition of the present invention.
[ organic titanium Compound ]
The resin composition of the present embodiment may contain an organic titanium compound. The resin composition can form a resin layer excellent in chemical resistance even when cured at a low temperature by containing an organic titanium compound.
Examples of the usable organic titanium compound include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in the following I) to VII).
I) Chelating titanium compound: among them, a chelate titanium compound having 2 or more alkoxy groups is more preferable in view of excellent storage stability of the resin composition and obtaining a good cured pattern. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium bis (n-butoxy) bis (2, 4-glutarate) diisopropoxide bis (2, 4-glutarate) titanium, titanium diisopropoxide bis (tetramethylheptanedioate) titanium, titanium diisopropoxide bis (ethylacetoacetate), and the like.
II) a titanium tetraalkoxide compound: examples of the titanium include tetra (n-butoxy) titanium, tetraethoxy titanium, tetra (2-ethylhexyl) titanium, tetraisobutoxy titanium, tetraisopropoxy titanium, tetramethoxy titanium, tetramethoxypropoxy titanium, tetramethylphenoxy titanium, tetra (n-nonoxy) titanium, tetra (n-propoxy) titanium, tetrastearoxy titanium, and tetra [ bis {2,2- (allyloxymethyl) propoxy } ] titanium.
III) titanocene compound: for example, pentamethylcyclopentadienyl trimethoxytitanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and the like.
IV) monoalkoxytitanium compounds: for example, titanium isopropoxide, such as dioctyl phosphate, and titanium isopropoxide, such as dodecylbenzenesulfonate.
V) titanium oxide compound: examples of the compound include titanium oxide bis (glutarate), titanium oxide bis (tetramethylpimelate), and titanium oxide phthalocyanine.
VI) titanium tetra acetylacetonate compound: for example, titanium tetraacetylacetonate.
VII) titanate coupling agent: for example, isopropyl tridecyl benzenesulfonyl titanate, etc.
Among them, the organic titanium compound is preferably at least 1 compound selected from the group consisting of the above-mentioned I) chelate titanium compound, II) tetraalkoxy titanium compound and III) titanocene compound, from the viewpoint of exhibiting more excellent chemical resistance. Particularly preferred are diisopropoxybis (ethylacetoacetate) titanium, tetra (n-butoxy) titanium and bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.
When the organic titanium compound is blended, the blending amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when 10 parts by mass or less, the composition is more excellent in storage stability.
[ antioxidant ]
The composition of the present invention may comprise an antioxidant. By containing an antioxidant as an additive, the tensile properties of the cured film and the adhesion to a metal material can be improved. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferred examples of the phenol compound include hindered phenol compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Further, the antioxidant can also preferably be a phosphorus-based antioxidant. Examples of phosphorus antioxidants include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphen-hepta-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4, 6,9, 11-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosphen-2-yl) oxy ] ethyl ] amine, and ethyl bis (2, 4-di-t-butyl-6-methylphenyl) phosphite. Examples of the commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50F, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (manufactured by ADEKA CORPORATION). The antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese patent No. 6268967, incorporated herein by reference. Furthermore, the compositions of the present invention may contain latent antioxidants as desired. As potential antioxidants, the following compounds may be mentioned: a compound which functions as an antioxidant by protecting a site functioning as an antioxidant with a protecting group and releasing the protecting group by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst. Examples of the potential antioxidant include compounds described in International publication No. 2014/021023, international publication No. 2017/030005, and Japanese patent application laid-open No. 2017-008219, which are incorporated herein by reference. Examples of commercial products of the latent antioxidant include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).
Examples of preferred antioxidants include 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol, and compounds represented by formula (3).
[ chemical formula 60]
In the general formula (3), R 5 Represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), R 6 An alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R is R 7 Represents a 1-to 4-valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.
The compound represented by formula (3) suppresses oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. Further, by the rust prevention effect on the metal material, oxidation of the metal can be suppressed.
In order to be able to act on both the resin and the metal material, k is more preferably an integer of 2 to 4. As R 7 Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silicon group, an alkoxy silicon group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, and a combination of these groups. Among them, alkyl ether, -NH-is preferable from the viewpoint of solubility in a developer and metal adhesion, and from the viewpoint of interaction with a resin and metal adhesion due to formation of a metal complex, More preferably-NH-.
Examples of the compound represented by the general formula (3) include, but are not limited to, the following structures.
[ chemical formula 61]
[ chemical formula 62]
[ chemical formula 63]
[ chemical formula 64]
The amount of the antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. By setting the addition amount to 0.1 part by mass or more, the effects of improving the tensile characteristics and the adhesion to the metal material are easily obtained even under a high-temperature and high-humidity environment, and by setting the addition amount to 10 parts by mass or less, for example, the sensitivity of the resin composition is improved by interaction with the photosensitive agent. The antioxidant may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the sum of the amounts thereof is preferably within the above-mentioned range.
[ anti-coagulant ]
The resin composition of the present embodiment may contain an anti-coagulant as necessary. Examples of the anti-caking agent include sodium polyacrylate.
In the present invention, 1 anticoagulant may be used alone, or 2 or more anticoagulants may be used in combination.
The composition of the present invention may or may not contain an anticoagulant, but when contained, the content of the anticoagulant is preferably 0.01 mass% or more and 10 mass% or less, more preferably 0.02 mass% or more and 5 mass% or less, relative to the total solid content mass of the composition of the present invention.
[ phenol Compounds ]
The resin composition of the present embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis-Z, bisP-EZ, tekP-4HBPA, trisP-HAP, trisP-PA, bisOCHP-Z, bisP-MZ, bisP-PZ, bisP-IPZ, bisOCP-IPZ, bisP-CP, bisRS-2P, bisRS-3P, bisP-OCHP, methyl Tris-FR-CR, bisRS-26X (trade name, honshu Chemical Industry Co., ltd.), BIP-PC, BIR-PTBP, BIR-BIPC-F (trade name, ASAHI YUKIZAI CORPORATION).
In the present invention, 1 kind of phenol compound may be used alone, or 2 or more kinds may be used in combination.
The composition of the present invention may or may not contain a phenolic compound, but when contained, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, relative to the total solid content mass of the composition of the present invention.
[ other Polymer Compounds ]
Examples of the other polymer compound include a silicone resin, a (meth) acrylic polymer copolymerized with (meth) acrylic acid, a novolak resin, a resol resin, a polyhydroxystyrene resin, and a copolymer of these. The other polymer compound may be modified body having a crosslinking group such as a hydroxymethyl group, an alkoxymethyl group, or an epoxy group introduced therein.
In the present invention, 1 or 2 or more other polymer compounds may be used alone or in combination.
The composition of the present invention may or may not contain other polymer compounds, but when contained, the content of other polymer compounds is preferably 0.01 mass% or more and 30 mass% or less, more preferably 0.02 mass% or more and 20 mass% or less, relative to the total solid content mass of the composition of the present invention.
< Properties of resin composition >
The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000mm 2 /s～12,000mm 2 S, more preferably 2,000mm 2 /s～10,000mm 2 S, more preferably 2,500mm 2 /s～8,000mm 2 And/s. When the amount is within the above range, a coating film having high uniformity can be easily obtained. For example 1,000mm 2 When it is not less than/s, it is easy to apply it with a film thickness of 12,000mm required as an insulating film for rewiring 2 When the ratio is not more than/s, a coating film excellent in the coating surface shape can be obtained.
< restriction of substances contained in resin composition >
The water content of the resin composition of the present invention is preferably less than 2.0 mass%, more preferably less than 1.5 mass%, and even more preferably less than 1.0 mass%. When the content is less than 2.0%, the storage stability of the resin composition is improved.
Examples of the method for maintaining the water content include adjusting the humidity under the storage conditions and reducing the porosity of the storage container during storage.
From the viewpoint of insulation properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, except for metals contained as a complex of an organic compound and a metal. When a plurality of metals are contained, the total of these metals is preferably within the above range.
Further, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following method can be mentioned: the raw material having a small metal content is selected as the raw material for forming the resin composition of the present invention, the raw material for forming the resin composition of the present invention is filtered by a filter, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation or the like is performed under a condition that contamination is suppressed as much as possible.
In the resin composition of the present invention, when the use as a semiconductor material is considered, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosiveness. Wherein the amount present in the state of halide ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion is preferably within the above range.
As a method for adjusting the halogen atom content, ion exchange treatment and the like are preferable.
As the container for containing the resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, a multilayer bottle having 6 kinds of 6 layers of resins constituting the inner wall of the container and a bottle having 6 kinds of resins and 7 layers of resins are preferably used for the purpose of suppressing the mixing of impurities into the raw material or the resin composition of the present invention. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351.
< cured product of resin composition >
By curing the resin composition of the present invention, a cured product of the resin composition can be obtained,
the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The curing of the resin composition is preferably performed by heating, and the heating temperature is more preferably in the range of 120 to 400 ℃, still more preferably in the range of 140 to 380 ℃, and particularly preferably in the range of 170 to 350 ℃. The form of the cured product of the resin composition is not particularly limited, and may be selected from films, rods, spheres, pellets, and the like according to the application. In the present invention, the cured product is preferably in the form of a film. The shape of the cured product can be selected by patterning the resin composition according to the use of the resin composition, such as forming a protective film on a wall surface, forming a through hole for conduction, adjusting impedance, electrostatic capacitance, or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film formed from the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage of the resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. The shrinkage ratio herein refers to the percentage of the volume change of the resin composition before and after curing, and can be calculated from the following formula.
Shrinkage [% ] =100- (volume after curing ≡volume before curing) ×100
< Property of cured product of resin composition >
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. At 70% or more, a cured product having excellent mechanical properties may be obtained.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ℃ or higher, more preferably 210 ℃ or higher, and still more preferably 230 ℃ or higher.
< preparation of resin composition >
The resin composition of the present invention can be prepared by mixing the above-described components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
The mixing may be performed by stirring blades, by a ball mill, by rotating a tank itself, or the like.
The temperature during mixing is preferably 10 to 30 ℃, more preferably 15 to 25 ℃.
In order to remove foreign matters such as dust and particles in the resin composition of the present invention, it is preferable to filter the resin composition by using a filter. The filter pore size is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the filter is made of polyethylene, HDPE (high density polyethylene) is more preferable. The filter may be a filter previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be connected in series or in parallel. When a plurality of filters are used, filters having different pore diameters or different materials may be used in combination. Examples of the connection method include the following: HDPE filters with a pore size of 1 μm were used as the first stage, HDPE filters with a pore size of 0.2 μm were used as the second stage, and the two were connected in series. Moreover, various materials may be filtered multiple times. When the filtration is performed a plurality of times, the filtration may be a cyclic filtration. Moreover, pressure filtration may be performed. When the pressure filtration is performed, for example, the pressure applied is 0.01MPa or more and 1.0MPa or less, preferably 0.03MPa or more and 0.9MPa or less, more preferably 0.05MPa or more and 0.7MPa or less, and still more preferably 0.O5MPa or more and 0.5MPa or less.
In addition to filtration using a filter, impurity removal treatment may be performed using an adsorbent. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent material. 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.
After filtration with the filter, the resin composition filled in the bottle may be further subjected to a step of deaeration by placing the resin composition under reduced pressure.
(method for producing cured product)
The method for producing a cured product of the present invention preferably includes a film formation step of applying a resin composition to a substrate to form a film.
The method for producing a cured product of the present invention further preferably includes the film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
The method for producing a cured product according to the present invention preferably includes at least one of the film forming step, the exposing step, the developing step, and a heating step of heating the pattern obtained in the developing step and a post-developing exposing step of exposing the pattern obtained in the developing step.
The production method of the present invention preferably further includes the film forming step and the step of heating the film.
The details of each step will be described below.
< film Forming Process >
The resin composition of the present invention can be used in a film forming step for forming a film on a substrate.
The method for producing a cured product of the present invention preferably includes a film formation step of applying a resin composition to a substrate to form a film.
[ substrate ]
The type of the substrate may be appropriately determined according to the application, and examples thereof include substrates for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, metal substrates such as quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, ni, cu, cr, fe (for example, any of substrates formed of metal and substrates formed with a metal layer by plating, vapor deposition, and the like), papers, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, electrode plates of Plasma Display Panels (PDP), and the like, without particular limitation. In the present invention, a substrate for semiconductor production is particularly preferable, and a silicon substrate, a Cu substrate, and a mold substrate are more preferable.
Further, the surface of these substrates may be provided with an adhesion layer, an oxide layer, or the like formed of Hexamethyldisilazane (HMDS), or the like.
The shape of the base material is not particularly limited, and may be circular or rectangular.
The size of the base material is, for example, 100 to 450mm, preferably 200 to 450mm in diameter in the case of a circular shape. In the case of rectangular shapes, the length of the short side is, for example, 100 to 1000mm, preferably 200 to 700mm.
As the base material, for example, a plate-like base material (substrate) is preferably used.
When a resin composition is applied to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer to form a film, the resin layer and the metal layer serve as a base material.
As a method for applying the resin composition of the present invention to a substrate, coating is preferable.
Specific examples of the application method include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. The spin coating method, the slit coating method, the spray coating method, or the inkjet method is more preferable from the viewpoint of film thickness uniformity, and the spin coating method and the slit coating method are preferable from the viewpoint of film thickness uniformity and productivity. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained. In addition, a coating method can be appropriately selected according to the shape of the substrate, and spin coating, spray coating, ink jet method, or the like is preferable in the case of a round substrate such as a wafer, and slit coating, spray coating, ink jet method, or the like is preferable in the case of a rectangular substrate. In the case of spin coating, for example, a spin speed of 500 to 3,500rpm can be applied for about 10 seconds to 3 minutes.
Further, a method of transferring a coating film formed by previously applying the above-described applying method to a temporary support onto a substrate can also be applied.
As the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of japanese patent application laid-open publication No. 2006-023696 or 0096 to 0108 of japanese patent application laid-open publication No. 2006-047592 can be preferably used in the present invention.
Further, a step of removing an excess film on the end portion of the base material may be performed. Examples of such a process include Edge Bead Rinse (EBR) and back surface rinse.
Furthermore, the following pre-wetting process may be employed: before the resin composition is applied to the substrate, various solvents are applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.
< drying Process >
The film may be subjected to a step of drying the formed film (layer) after the film forming step (layer forming step) to remove the solvent.
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
The drying step is preferably performed after the film formation step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, and even more preferably 90 to 110 ℃. Further, drying may be performed by decompression. The drying time may be exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.
< Exposure procedure >
The film may be subjected to an exposure step of selectively exposing the film.
That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film forming step.
Selective exposure refers to exposing a portion of the film. By performing selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured, and is preferably 50 to 10,000mJ/cm, for example, in terms of an exposure energy conversion at a wavelength of 365nm 2 More preferably 200 to 8,000mJ/cm 2 。
The exposure wavelength can be appropriately determined in the range of 190 to 1,000nm, preferably 240 to 550nm.
As the exposure wavelength, there may be mentioned (1) a semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broadband (g, h, 3 wavelengths of i-rays), (4) an excimer laser, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), F 2 Excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532nm, third harmonic 355nm of YAG laser, etc. With respect to the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferable, and among them, exposure based on i-rays is preferable. Thus, particularly high exposure sensitivity can be obtained.
The method of exposure is not particularly limited as long as at least a part of the film formed from the resin composition of the present invention is exposed, and examples thereof include exposure using a photomask, exposure by a laser direct imaging method, and the like.
< post-exposure heating Process >
The film may be subjected to a heating step (post-exposure heating step) after exposure.
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
The post-exposure heating step may be performed after the exposure step and before the development step.
The heating temperature in the post-exposure heating step is preferably 50 to 140 ℃, more preferably 60 to 120 ℃.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and even more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the maximum heating temperature.
The temperature rise rate may be appropriately changed during the heating process.
The heating method in the post-exposure heating step is not particularly limited, and a known heating plate, oven, infrared heater, or the like can be used.
In addition, the heating is preferably performed in an atmosphere having a low oxygen concentration by passing an inert gas such as nitrogen, helium, or argon.
< developing Process >
The exposed film may be subjected to a developing step of developing with a developer to form a pattern.
That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step with a developer to form a pattern. By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern.
Here, the development of the non-exposed portion of the film removed by the development step is referred to as negative development, and the development of the exposed portion of the film removed by the development step is referred to as positive development.
[ developer solution ]
As the developer used in the developing step, an aqueous alkali solution or a developer containing an organic solvent is exemplified.
When the developer is an aqueous alkali solution, examples thereof include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltrimentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis (2-hydroxyethyl) ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.3 to 3 mass% based on the total amount of the developer.
When the developer contains an organic solvent, examples of the esters 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, epsilon-caprolactone, delta-valerolactone, and alkyl alkoxyacetate (for example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (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.), ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene glycol monomethyl ether acetate (PGMFA), 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, and the like, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, isopropanol, diethylene glycol, methyl butanol, N-butyl glycol, methyl pyrrolidone, N-methyl pyrrolidone, and the like, and as methyl-pyrrolidone, and the like, and as alcohols, and as methyl-N-butyl amide, and the like, are preferable.
When the developer contains an organic solvent, 1 or 2 or more organic solvents can be used in combination. In the present invention, in particular, a developer containing at least 1 selected from cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferable, a developer containing at least 1 selected from cyclopentanone, γ -butyrolactone, and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.
When the developing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the developing solution. The content may be 100% by mass.
The developer may further contain other components.
Examples of the other components include a known surfactant and a known defoaming agent.
[ method for supplying developer ]
The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing a substrate on which a film is formed in a developer, a spin-on immersion developing method of supplying a developer to a film formed on a substrate by a nozzle, or a method of continuously supplying a developer. The type of the nozzle is not particularly limited, and examples thereof include a direct current nozzle, a shower nozzle, a spray nozzle, and the like.
The method of supplying the developer with the direct current nozzle or the method of continuously supplying the developer with the spray nozzle is preferable from the viewpoints of the permeability of the developer, the removability of the non-image portion, and the efficiency in production, and the method of supplying the developer with the spray nozzle is more preferable from the viewpoints of the permeability of the developer to the image portion.
Further, the following steps may be adopted: the process may be repeated a plurality of times by rotating the substrate to remove the developer from the substrate after the developer is continuously supplied by the direct current nozzle, and by rotating the substrate to remove the developer from the substrate after the developer is continuously supplied again by the direct current nozzle after the spin-drying.
As a method for supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of holding the developer on the substrate in a substantially stationary state, a step of vibrating the developer on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be used.
The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, and may be preferably 10 to 45 ℃, more preferably 18 to 30 ℃.
In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse solution. Further, a method of supplying a rinse solution or the like before the developer in contact with the pattern is not completely dried may be employed.
[ flushing liquid ]
When the developer is an aqueous alkali solution, water can be used as the rinse liquid, for example. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.
When the rinse liquid contains an organic solvent, examples of the organic solvent include ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-alkoxymethyl 2-alkoxypropionate, methyl 2-alkoxymethyl 2-ethoxypropionate, methyl 2-ethoxymethyl 2-alkoxymethyl 2-ethoxypropionate, etc.), and the like (e.g., methyl 2-ethoxypropionate, methyl 2-ethoxymethyl 2-alkoxypropionate, etc.), and the like, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, isopropanol, diethylene glycol, methyl butanol, N-butyl glycol, methyl pyrrolidone, N-methyl pyrrolidone, and the like, and as methyl amides, and the like, and as ketones, and as preferred examples.
When the rinse liquid contains an organic solvent, the organic solvent may be used in an amount of 1 or 2 or more kinds thereof may be used in combination. In the present invention, particularly preferred are cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, more preferred are cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, and still more preferred are cyclohexanone and PGMEA.
When the rinse liquid contains an organic solvent, it is preferable that 50 mass% or more of the rinse liquid is an organic solvent, more preferably 70 mass% or more is an organic solvent, and still more preferably 90 mass% or more is an organic solvent. Further, the rinse solution may be 100 mass% organic solvent.
The rinse solution may also contain other ingredients.
Examples of the other components include a known surfactant and a known defoaming agent.
[ method for supplying rinse solution ]
The method of supplying the rinse liquid is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing a substrate in a rinse solution, a method of supplying a rinse solution to a substrate by spin-coating immersion, a method of supplying a rinse solution to a substrate by a shower head, a method of continuously supplying a rinse solution to a substrate by a direct-current nozzle or the like.
From the viewpoints of the permeability of the rinse liquid, the removability of the non-image portion, and the efficiency in production, a method of supplying the rinse liquid by using a spray nozzle, a direct-current nozzle, a spray nozzle, or the like is preferable, and a method of continuously supplying the rinse liquid by using a spray nozzle is more preferable from the viewpoint of the permeability of the rinse liquid to the image portion. The type of the nozzle is not particularly limited, and examples thereof include a direct current nozzle, a shower nozzle, a spray nozzle, and the like.
That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the exposed film through a direct-current nozzle, and more preferably a step of supplying a rinsing liquid through a spray nozzle.
As a method for supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the substrate, a step of holding the rinse liquid on the substrate in a substantially stationary state, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be used.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinse liquid during the rinsing is not particularly limited, and the rinsing may be preferably performed at 10 to 45 ℃, and more preferably at 18 to 30 ℃.
< heating Process >
The pattern obtained by the development step (the pattern after the rinsing step in the case of performing the rinsing step) may be subjected to a heating step of heating the pattern obtained by the development.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.
The method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the development step or a film obtained by the film forming step.
In the heating step, the resin such as polyimide precursor is cyclized into the resin such as polyimide.
Further, crosslinking of unreacted crosslinkable groups in the specific resin or the crosslinking agent other than the specific resin is also performed.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ℃, more preferably 150 to 350 ℃, still more preferably 150 to 250 ℃, still more preferably 160 to 250 ℃, and particularly preferably 160 to 230 ℃.
The heating step is preferably the following step: the cyclization reaction of the polyimide precursor is promoted in the pattern by the action of a base or the like generated from the base generator by heating.
The heating in the heating step is preferably performed at a heating rate of 1 to 12 ℃/min from the temperature at the start of heating to the maximum heating temperature. The temperature rise rate is more preferably 2 to 10℃per minute, and still more preferably 3 to 10℃per minute. The temperature rise rate is set to 1 ℃/min or more, whereby excessive volatilization of the acid or solvent can be prevented while ensuring productivity, and the residual stress of the cured product can be relaxed by setting the temperature rise rate to 12 ℃/min or less.
In the case of an oven capable of rapid heating, the heating is preferably performed at a temperature rise rate of 1 to 8 ℃/sec, more preferably 2 to 7 ℃/sec, and still more preferably 3 to 6 ℃/sec, from the temperature at the start of heating to the highest heating temperature.
The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, still more preferably 25 to 120 ℃. The temperature at the start of heating means the temperature at the start of the step of heating to the highest heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably increased from a temperature lower by 30 to 200 ℃ than the boiling point of the solvent contained in the resin composition of the present invention.
The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, still more preferably 15 to 240 minutes.
In particular, in forming the multilayer laminate, the heating temperature is preferably 30 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 100 ℃ or higher, and particularly preferably 120 ℃ or higher, from the viewpoint of interlayer adhesiveness.
The upper limit of the temperature is preferably 350℃or lower, more preferably 250℃or lower, and still more preferably 240℃or lower.
The heating may be performed in stages. As an example, the following procedure may be performed: heating from 25 ℃ to 120 ℃ at 3 ℃/min and holding at 120 ℃ for 60 minutes, heating from 120 ℃ to 180 ℃ at 2 ℃/min and holding at 180 ℃ for 120 minutes. Further, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. Such a pretreatment step can improve the film characteristics. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in 2 stages or more, for example, the pretreatment in stage 1 may be performed at 100 to 150 ℃ and the pretreatment in stage 2 may be performed at 150 to 200 ℃.
Further, the cooling may be performed after the heating, and the cooling rate at this time is preferably 1 to 5 ℃/min.
The heating step is preferably performed under a reduced pressure in which an inert gas such as nitrogen, helium, or argon is circulated, for example, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50ppm (volume ratio) or less, more preferably 20ppm (volume ratio) or less.
The heating method in the heating step is not particularly limited, and examples thereof include a heating plate, an infrared oven, an electrothermal oven, a hot air oven, an infrared oven, and the like.
< post-development exposure Process >
The pattern obtained by the development step (the pattern after the rinsing step in the case of performing the rinsing step) may be subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction of cyclizing a polyimide precursor or the like by the light-sensitive base generator, a reaction of releasing an acid-decomposable group by the light-sensitive base generator, or the like can be promoted.
In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, and preferably all of the pattern is exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000mJ/cm as calculated by the exposure energy conversion at a wavelength at which the photosensitive compound has sensitivity 2 More preferably 100 to 15,000mJ/cm 2 。
The post-development exposure step can be performed using, for example, the light source in the exposure step, and preferably using broadband light.
< Metal layer Forming Process >
The pattern obtained by the development step (preferably, at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern.
That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably, at least one of a heating step and a post-developing exposure step is performed).
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, tungsten, tin, silver, and alloys containing these metals, more preferably copper and aluminum, and still more preferably copper.
The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese patent application laid-open No. 2007-157879, japanese patent application laid-open No. 2001-521288, japanese patent application laid-open No. 2004-214501, japanese patent application laid-open No. 2004-101850, U.S. Pat. No. 7888181B2, and U.S. Pat. No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift off (lift off), electroplating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electroplating are combined can be cited. A preferred embodiment of plating includes plating using a copper sulfate plating solution or a copper cyanide plating solution.
The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, in terms of the thickest part.
< use >
Examples of the field to which the method for producing a cured product of the present invention or the cured product of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, there are a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), a case where a pattern is formed on an insulating film for practical mounting purposes such as those described above by etching, and the like. For these uses, for example, reference can be made to Science & Technology co., ltd, "high functionalization of polyimide and application Technology of application", release of polyimide material base and development "11 th 2011", release of polyimide material base and application "NTS, 8 th 2010, etc., of the kaki ben yan min/prison, CMC technical library.
The method for producing a cured product of the present invention and the cured product of the present invention can also be used for producing a plate surface such as an offset plate surface or a screen plate surface, use of a molded part in etching, production of a protective paint and a dielectric layer in electronics, particularly microelectronics, and the like.
(laminate and method for producing laminate)
The laminate of the present invention is a structure having a plurality of layers formed from the cured product of the present invention.
The laminate of the present invention may be a laminate comprising 2 or more layers of cured products, or may be a laminate comprising 3 or more layers.
Of the layers of the cured product of 2 or more layers contained in the laminate, at least 1 layer is a layer of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying the shrinkage, it is also preferable that all of the layers of the cured product contained in the laminate are layers of the cured product of the present invention.
That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes the step of repeating the method for producing a cured product of the present invention a plurality of times.
The laminate of the present invention includes 2 or more layers of a cured product, and preferably includes a metal layer between any of the layers of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer formed of a cured product between the methods for producing a cured product that are carried out a plurality of times. The preferable mode of the metal layer forming step is as described above.
As the laminate, for example, a laminate having a layer structure in which at least 3 layers of a layer formed of a first cured product, a metal layer, and a layer formed of a second cured product are laminated in this order is preferable.
The layer formed of the first cured product and the layer formed of the second cured product are each preferably a layer formed of the cured product of the present invention. The resin composition of the present invention for forming a layer formed of the first cured product and the resin composition of the present invention for forming a layer formed of the second cured product may have the same composition or may have a composition different from each other. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a rewiring layer.
< lamination Process >
The method for producing a laminate of the present invention preferably includes a lamination step.
The lamination step is a series of steps including at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step, in this order again, on the surface of the pattern (resin layer) or the metal layer. The film formation step (a) and at least one of the heating step and the post-development exposure step may be repeated. Further, the method may include (e) a metal layer forming step after at least one of the heating step and the post-development exposure step. The lamination step may obviously further include the above-described drying step or the like as appropriate.
When the lamination step is further performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, after the heating step, or after the metal layer formation step. As the surface activation treatment, a plasma treatment is exemplified. Details of the surface activation treatment will be described later.
The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, the resin layer is preferably a structure of 2 or more and 20 or less layers, more preferably a structure of 2 or more and 9 or less layers, such as a resin layer/metal layer/resin layer/metal layer.
The composition, shape, film thickness, etc. of the layers may be the same or different.
In the present invention, the following modes are preferable: in particular, after the metal layer is provided, a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, the method includes a method in which (a) the film forming step, (b) the exposure step, (c) the developing step, (d) at least one of the heating step and the post-developing exposure step, and (e) the metal layer forming step are repeated in this order, or a method in which (a) the film forming step, (d) at least one of the heating step and the post-developing exposure step, and (e) the metal layer forming step are repeated in this order. The resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) and the metal layer formation step of the present invention.
(surface activation treatment Process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface-activating at least a part of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step is performed on the resin composition layer after the development step (preferably after at least one of the heating step and the post-development exposure step).
The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the resin composition layer after exposure, or may be performed on at least a part of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and more preferably, a part or the whole of the region of the metal layer where the resin composition layer is formed is surface-activated. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) provided on the surface thereof can be improved.
The surface activation treatment is preferably performed on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer or the resin layer provided on the surface subjected to the surface activation treatment can be improved. In particular, in the case of performing negative development or the like, when the resin composition layer is cured, the resin composition layer is less likely to be damaged by the surface treatment, and adhesion is easily improved.
The surface activation treatment may be specifically plasma treatment, corona discharge treatment, CF-based treatment, or the like from various source gases (oxygen, hydrogen, argon, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, or the like) 4 /O 2 、NF 3 /O 2 、SF 6 、NF 3 、NF 3 /O 2 The etching treatment, the surface treatment by Ultraviolet (UV) ozone method, the treatment of immersing in an aqueous hydrochloric acid solution to remove an oxide film and then immersing in an organic surface treating agent containing a compound having at least 1 of an amino group and a thiol group, and the mechanical roughening treatment using a brush are selected, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a source gas is particularly preferable. In the case of corona discharge treatment, the energy is preferably 500 to 200,000J/m 2 More preferably 1000 to 100,000J/m 2 Most preferably from 10,000 to 50,000J/m 2 。
(semiconductor device and method for manufacturing the same)
The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.
The present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product of the present invention or the method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used for forming an interlayer insulating film for a re-wiring layer, reference is made to the descriptions in paragraphs 0213 to 0218 and the description in fig. 1 of japanese patent application laid-open publication 2016-027357, which are incorporated herein by reference.
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment order, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass references.
< Synthesis of Compound B >
[ Synthesis of SA-1 ]
In a flask equipped with a stirrer and a condenser, 13.0g (100 mmol) of 2-hydroxyethyl methacrylate (Tokyo Chemical Industry co., ltd.) and 0.001g of p-methoxyphenol (Tokyo Chemical Industry co., ltd.) were dissolved in 60mL of tetrahydrofuran, and then stirred at 25 ℃. Subsequently, 11.9g (100 mmol) of phenyl isocyanate (Tokyo Chemical Industry co., ltd.) was added dropwise over 1 hour, and then the mixture was heated to 50 ℃ and stirred for 4 hours. Then, it was dissolved in 800mL of ethyl acetate and transferred to a separating funnel. Then, the mixture was washed with dilute hydrochloric acid, sodium hydrogencarbonate and saturated brine in this order, and the solvent was removed by using an evaporator to obtain 18g of SA-1. SA-1 is presumed to be a compound represented by the following formula SA-1. By passing through 1 The H-NMR spectrum confirmed SA-1.
[ Synthesis of SA-2 to SA-22 ]
SA-2 to SA-22 were synthesized in the same manner as in the synthesis of SA-1, except that alcohol (2-hydroxyethyl methacrylate) and isocyanate (phenyl isocyanate) were changed in the synthesis of SA-1. SA-2 to SA-22 are presumed to be compounds represented by the following formulas SA-2 to SA-22, respectively.
[ Synthesis of SA-23 ]
In a flask equipped with a stirrer and a condenser, 5.36g (50 mmol) of N-methylaniline (Tokyo Chemical Industry Co., ltd.), 4.51g (55 mmol) of N-methylimidazole (Tokyo Chemical Industry Co., ltd.), and 0.001g of p-methoxyphenol (Tokyo Chemical Industry Co., ltd.) were dissolved in 80mL of chloroform, and stirred at 10 to 20 ℃. Subsequently, 9.77g (52.5 mmol) of diallyl dicarbonate (Tokyo Chemical Industry co., ltd.) was added, followed by stirring at 10 to 20℃for 5 hours. Then, 300mL of chloroform was added and the mixture was transferred to a separating funnel, and the mixture was washed with dilute hydrochloric acid, sodium hydrogencarbonate and saturated brine in this order, and the solvent was removed by using an evaporator to obtain 7.2g of SA-23. SA-23 is presumed to be a compound represented by the following formula SA-23. By passing through 1 The H-NMR spectrum confirmed SA-23.
[ Synthesis of SA-24 to SA-25 ]
SA-24 to SA-25 were synthesized by the same method as SA-23, except that the starting compounds were appropriately changed. SA-24 to SA-25 are presumed to be compounds represented by the following formulas SA-24 to SA-25, respectively.
[ chemical formula 65]
[ chemical formula 66]
< synthesis example a-1: synthesis of polyimide precursor (A-1)
21.2g (68.1 mmol) of 4,4 '-oxybisphthalic dianhydride, 17.8g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 22.8g (289 mmol) of pyridine and 85g of diethylene glycol dimethyl ether were mixed and stirred at a temperature of 60℃for 6 hours to produce a diester of 4,4' -oxybisphthalic acid and 2-hydroxyethyl methacrylate. Then, after the mixture was cooled to-20 ℃, 16.7g (140 mmol) of thionyl chloride was added dropwise over 90 minutes, and stirred for 2 hours, a white precipitate of pyridine hydrochloride was obtained. Then, 21.1g (57.2 mmol) of 4,4' -bis (4-aminophenoxy) biphenyl was added dropwise to 100mL of NMP over 1 hour. Next, 10.0g (217 mmol) of ethanol was 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 in 4 liters of water for 30 minutes again and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 3 days to obtain a polyimide precursor (a-1). The polyimide precursor A-1 obtained had a weight average molecular weight of 18,100 and a number average molecular weight of 8,400.
The structure of A-1 is assumed to be represented by the following formula (A-1).
[ chemical formula 67]
< synthesis example a-2: synthesis of polyimide precursor (A-2)
10.6g (34.1 mmol) of 4,4' -oxybisphthalic acid dianhydride, 10.0g (34 mmol) of 4,4' -diphthalic acid dianhydride, 17.8g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 22.8g (289 mmol) of pyridine and 85g of diethylene glycol dimethyl ether were mixed and stirred at a temperature of 60℃for 6 hours to produce a diester of 4,4' -oxybisphthalic acid and 2-hydroxyethyl methacrylate. Then, by SOCl 2 After the obtained diester was chlorinated, 4' -bis (4-aminophenoxy) biphenyl was converted into a polyimide precursor in the same manner as in Synthesis example A-1, and a polyimide precursor (A-2) was obtained in the same manner as in Synthesis example A-1. The polyimide precursor had a weight average molecular weight of 17,600 and a number average molecular weight of 7,800. The structure of A-2 is assumed to be represented by the following formula (A-2).
[ chemical formula 68]
< synthesis example a-3: synthesis of polyimide precursor (A-3)
[ Synthesis of polyimide precursor from 4,4 '-oxydiphthalic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: polyimide precursor having radical polymerizable group) ]
20.0g (64.5 mmol) of 4,4 '-oxybisphthalic dianhydride (dried at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 mmol) of pyridine and 100g of diethylene glycol dimethyl ether were mixed and stirred at 60℃for 18 hours to produce a biphthalic acid-2-hydroxyethyl methacrylate-4, 4' -oxybisphthalate mixtureAn ester. Then, by SOCl 2 After the obtained diester was chlorinated, the 4,4' -diaminodiphenyl ether was converted into a polyimide precursor in the same manner as in Synthesis example A-5, and a polyimide precursor (A-3) was obtained in the same manner as in Synthesis example A-5. The polyimide precursor had a weight average molecular weight of 19,600.
The structure of A-3 is assumed to be represented by the following formula (A-3).
[ chemical formula 69]
< synthesis example a-4: synthesis of polyimide precursor (A-4)
[ Synthesis of polyimide precursor (A-4: polyimide precursor having radical polymerizable group) from 4,4' -oxydiphthalic dianhydride, 4' -diamino-2, 2' -dimethylbiphenyl (o-tolidine) and 2-hydroxyethyl methacrylate ]
20.0g (64.5 mmol) of 4,4 '-oxybisphthalic anhydride (dried at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 mmol) of pyridine and 100g of diethylene glycol dimethyl ether were mixed and stirred at 60℃for 18 hours to produce a diester of 4,4' -oxybisphthalic acid and 2-hydroxyethyl methacrylate. Then, by SOCl 2 After the obtained diester was chlorinated, the polyimide precursor (A-4) was obtained in the same manner as in Synthesis example A-5, by converting 4,4 '-diamino-2, 2' -dimethylbiphenyl into a polyimide precursor in the same manner as in Synthesis example A-5. The polyimide precursor had a weight average molecular weight of 23, 500.
The structure of A-4 is assumed to be represented by the following formula (A-4).
[ chemical formula 70]
< synthesis example a-5: synthesis of polyimide precursor (A-5)
[ A-5: synthesis of polyimide precursor resin A-5 from oxydiphthalic anhydride, 4 '-diphthalic anhydride, 2-hydroxyethyl methacrylate, and 4,4' -diaminodiphenyl ether
In a dry reactor equipped with a stirrer, condenser and a flat-bottom joint (joint) with an internal thermometer, 9.49g (32.25 mmol) of 4,4' -diphthalic anhydride and 10.0g (32.25 mmol) of oxydiphthalic anhydride were suspended in 140mL of diglyme while removing moisture. 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 0.05g of pure water and 10.7g (135 mmol) of pyridine were continuously added, and the mixture was stirred at 60℃for 18 hours. Next, after cooling the mixture to-20 ℃, 16.1g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Subsequently, the mixture was warmed to room temperature and stirred for 2 hours, and then 9.7g (123 mmol) of pyridine and 25mL of N-methylpyrrolidone (NMP) were added thereto to obtain a transparent solution. Next, a solution obtained by dissolving 11.8g (58.7 mmol) of 4,4' -diaminodiphenyl ether in 100mL of NMP was added dropwise over 1 hour. Next, 5.6g (17.5 mmol) of methanol and 0.05g of 3, 5-di-t-butyl-4-hydroxytoluene 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 in 4 liters of water for 30 minutes again and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 3 days to obtain a polyimide precursor (a-5). The weight average molecular weight of the obtained polyimide precursor A-5 was 23,800, and the number average molecular weight was 10,400.
The structure of A-5 is assumed to be represented by the following formula (A-5).
[ chemical formula 71]
Synthesis example A-6 ]
[ A-6: synthesis of polyimide precursor from 4,4 '-oxydiphthalic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-6: polyimide precursor having radical polymerizable group)
155.1g of 4,4' -oxybisphthalic anhydride (ODPA) was placed in a separate flask, and 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of gamma-butyrolactone were added. 79.1g of pyridine was added while stirring at room temperature, whereby a reaction mixture was obtained. After the completion of the heat generation by the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 16 hours.
Then, a solution of 206.3g of Dicyclohexylcarbodiimide (DCC) dissolved in 180ml of γ -butyrolactone was added to the reaction mixture over 40 minutes while stirring under ice-cooling. Subsequently, 93.0g of 4,4' -diaminodiphenyl ether was added to a suspension of 350ml of gamma-butyrolactone with stirring over a period of 60 minutes. After stirring at room temperature for 2 hours, 30ml of ethanol was added thereto and stirred for 1 hour. Thereafter, 400ml of gamma-butyrolactone was added. The precipitate formed in the reaction mixture was obtained by filtration, and a reaction solution was obtained.
The obtained reaction solution was added to 3 liters of ethanol, and a precipitate composed of a crude polymer was formed. The crude polymer thus produced was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran, whereby a crude polymer solution was obtained. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and then subjected to vacuum drying, whereby polymer A-6 was obtained in the form of a powder. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 24,000.
Synthesis example A-7 ]
[ Synthesis of polyimide precursor from 3,3', 4' -biphenyltetracarboxylic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-7: polyimide precursor having radical polymerizable group) ]
In Synthesis example 6, a reaction was carried out in the same manner as in Synthesis example A-6 except that 147.1g of 3,3', 4' -biphenyltetracarboxylic dianhydride was used in place of 155.1g of 4,4' -oxydiphthalic dianhydride, thereby obtaining a polymer A-7. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,900.
< Synthesis example A-8>
In a flask equipped with a stirrer and a condenser, 19.19g (36.7 mmol) of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (Tokyo Chemical Industry co., ltd.) was mixed, 0.01g of 4-methoxyphenol (Tokyo Chemical Industry co., ltd.) was mixed with 21.98g (75 mmol) of CS-1 (the above-described synthetic product), 12.92g (163 mmol) of pyridine, 40.0g of diethylene glycol dimethyl ether (Tokyo Chemical Industry Co., ltd.) was stirred at a temperature of 60℃for 6 hours. Then, after the mixture was cooled to-20 ℃, 9.19g (76.3 mmol) of thionyl chloride was added dropwise over 90 minutes, and stirred for 2 hours. Subsequently, 25mL of N-methylpyrrolidone (NMP) was added thereto, and a solution obtained by dissolving 6.11g (30.5 mmol) of 4,4' -diaminodiphenyl ether in 100mL of NMP was added dropwise over 2 hours. Subsequently, 16.9g (367 mmol) of ethanol was 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 in 4 liters of water for 30 minutes again and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ℃ for 2 days under reduced pressure to obtain a polyimide precursor (a-8). The weight average molecular weight of the obtained polyimide precursor A-8 was 30,100, and the number average molecular weight was 13,800.
The structure of A-8 is assumed to be represented by the following formula (A-8).
[ chemical formula 72]
< synthesis example a-9: synthesis of polyimide ]
In a flask equipped with a condenser and a stirrer, 26.0g (50 mmol) of 4,4'- (4, 4' -isopropylidenediphenoxy) bis (phthalic anhydride) (Tokyo Chemical Industry co., ltd.) and 0.02g of 2, 6-tetramethylpiperidine 1-oxyl (Tokyo Chemical Industry co., ltd.) were dissolved in 120.0g of N-methylpyrrolidone (NMP) while removing water. Next, 11.9g (45 mmol) of diamine (AA-1) described below was added thereto, and the mixture was stirred at 25℃for 3 hours and at 45℃for 3 more hours. Subsequently, 15.8g (200 mmol) of pyridine, 12.8g (125 mmol) of acetic anhydride, and 50g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80℃for 3 hours, and 50g of N-methylpyrrolidone (NMP) was added and diluted.
The reaction solution was precipitated in 1 liter of methanol and stirred at 3000rpm for 15 minutes. The resin was removed by filtration, stirred in 1 liter of methanol for a further 30 minutes and filtered again. The obtained resin was dried at 40℃under reduced pressure for 1 day to obtain polyimide A-9. The molecular weight of a-9 was mw=21,000, mn=9,100.
The structure of polyimide A-9 is assumed to be represented by the following formula (A-9).
[ chemical formula 73]
Synthesis example AA-1: synthesis of diamine AA-1
In a flask equipped with a condenser and a stirrer, 26.0g (0.2 mol) of 2-hydroxyethyl methacrylate (FUJIFILM Wako Pure Chemical Corporation system) and 17.4g (0.22 mol) of dehydrated pyridine (FUJIFILM Wako Pure Chemical Corporation system) were dissolved in 78g of ethyl acetate, and the mixture was cooled to 5℃or lower. Next, 48.4g (0.21 mol) of 3, 5-dinitrobenzoyl chloride (Tokyo Chemical Industry co., ltd.) was dissolved in 145g of ethyl acetate, and the solution was added dropwise to the flask over 1 hour using a dropping funnel. After the completion of the dropwise addition, the mixture was stirred at 10℃or lower for 30 minutes, heated to 25℃and stirred for 3 hours. Subsequently, the reaction mixture was treated with ethyl acetate (CH) 3 COOEt) 600mL was diluted and transferred to a liquid-separating funnelThe bucket was washed with 300mL of water, 300mL of saturated sodium bicarbonate water, 300mL of diluted hydrochloric acid, and 300mL of saturated brine in this order. After washing in separate liquid, 30g of magnesium sulfate was dried, concentrated by an evaporator and dried in vacuum to obtain 61.0g of dinitro (A-1).
To a flask equipped with a condenser and a stirrer, 27.9g (500 mmol) of reduced iron (FUJIFILM Wako Pure Chemical Corporation g), 5.9g (110 mmol) of ammonium chloride (FUJIFILM Wako Pure Chemical Corporation g), 3.0g (50 mmol) of acetic acid (FUJIFILM Wako Pure Chemical Corporation g), and 0.03g of 2, 6-tetramethylpiperidine 1-oxyl (Tokyo Chemical Industry co., ltd.) were weighed out, and 200mL of isopropyl alcohol (IPA) and 30mL of pure water were added and stirred.
Then, 16.2g of the dinitro (A-1) was added thereto over 1 hour and stirred for 30 minutes. Then, the outside temperature was raised to 85℃and stirred for 2 hours, cooled to 25℃or lower, and then filtered using Celite (registered trademark). The filtrate was concentrated by rotary evaporator and dissolved in 800mL of ethyl acetate. This was transferred to a separating funnel, washed 2 times with 300mL of saturated sodium bicarbonate water, and washed sequentially with 300mL of water and 300mL of saturated brine. After washing in a liquid, 30g of magnesium sulfate was dried, concentrated by an evaporator and dried in vacuo to obtain 11.0g of diamine (AA-1).
[ chemical formula 74]
< Synthesis of comparative Compound Cmp-1 >
In a flask equipped with a stirrer and a condenser, 10.2g (100 mmol) of 1-hexanol (Tokyo Chemical Industry co., ltd.) and 0.001g of p-methoxyphenol (Tokyo Chemical Industry co., ltd.) were dissolved in 60mL of tetrahydrofuran, and then stirred at 25 ℃. Next, 11.9g (100 mmol) of phenyl isocyanate (Tokyo Chemical Industry Co., ltd.) was added dropwise over 1 hourThe temperature was raised to 50℃and stirred for 4 hours. Then, it was dissolved in 800mL of ethyl acetate and transferred to a separating funnel. Then, the mixture was washed with dilute hydrochloric acid, sodium hydrogencarbonate and saturated brine in this order, and the solvent was removed by using an evaporator to obtain 15g of Cmp-1. The structure of Cmp-1 is assumed to be represented by the following formula (Cmp-1). By passing through 1 The H-NMR spectrum confirmed to be Cmp-1.
[ chemical formula 75]
< Synthesis of comparative Compound Cmp-2 >
In a flask equipped with a stirrer and a condenser, 10.2g (100 mmol) of 1-hexanol (Tokyo Chemical Industry co., ltd.) and 0.001g of p-methoxyphenol (Tokyo Chemical Industry co., ltd.) were dissolved in 80mL of tetrahydrofuran, and then stirred at 25 ℃. Next, 15.5g (100 mmol) of Karenz MOI (manufactured by SHOWA DENKO K.K.) was added dropwise over 1 hour, and the mixture was heated to 50℃and stirred for 4 hours. Then, it was dissolved in 800mL of ethyl acetate and transferred to a separating funnel. Then, the mixture was washed with dilute hydrochloric acid, sodium hydrogencarbonate and saturated brine in this order, and the solvent was removed by using an evaporator to obtain 19.5g of Cmp-2. The structure of Cmp-2 is assumed to be represented by the following formula (Cmp-2). By passing through 1 The H-NMR spectrum confirmed to be Cmp-2.
[ chemical formula 76]
< examples and comparative examples >
In each example, the components described in the following table were mixed, respectively, to thereby obtain each resin composition. In each comparative example, the ingredients described in the following table were mixed, and each comparative composition was obtained.
Specifically, the content of each component described in the table is set to the amount (parts by mass) described in the column "addition amount" of each column in the table.
The obtained resin composition and comparative composition were subjected to pressure filtration using a polytetrafluoroethylene filter having a pore width of 0.5. Mu.m.
In the table, "-" indicates that the composition does not contain any corresponding components.
TABLE 1
TABLE 2
The details of the components described in the table are as follows.
[ resin (cyclized resin or precursor thereof) ]
A-1 to A-9: a-1 to A-9 synthesized above
[ Compound B or Compound for comparison ]
SA-1 to SA-25: the above synthetic product (Compound B)
Cmp-1: the above-mentioned synthetic product (comparative compound)
Cmp-2: the above-mentioned synthetic product (comparative compound)
[ polymerization initiators (all trade names) ]
OXE-01: IRGACURE OXE 01 (manufactured by BASF corporation)
OXE-02: IRGACURE OXE 02 (manufactured by BASF corporation)
[ alkali-generating agent ]
D-1 to D-2: compounds of the structure
D-3: WPBG-027 (FUJIFILM Wako Pure Chemical Corporation)
[ chemical formula 77]
[ migration inhibitor ]
E-1 to E-6: compounds of the structure
[ chemical formula 78]
[ Metal adhesion improver ]
F-1 to F-3: compounds of the structure
[ chemical formula 79]
[ polymerizable Compound (trade name in each case) ]
SR-209: SR-209 (Sartomer Company, manufactured by Inc)
SR-231: SR-231 (Sartomer Company, manufactured by Inc)
DPE-400: BLEMER DPE-400 (NOF CORPORATION)
ADPH: dipentaerythritol hexaacrylate (Shin-Nakamura Chemical Co., ltd.)
[ polymerization inhibitor ]
H-1:1, 4-benzoquinone
H-2: 4-methoxyphenol
H-3:1, 4-dihydroxybenzene
H-4: compounds of the structure
[ chemical formula 80]
[ other additives ]
I-1: n-phenyl diethanolamine (Tokyo Chemical Industry Co., ltd.)
[ solvent ]
DMSO: dimethyl sulfoxide
GBL: gamma-butyrolactone
NMP: n-methylpyrrolidone
In the table, "DMSO/GBL" means that a solvent in which DMSO and GBL are mixed at a mixing ratio (mass ratio) of DMSO: gbl=80:20 was used.
< evaluation >
[ evaluation of elongation at Break ]
In each of examples and comparative examples, a resin composition layer was formed by applying a resin composition or a composition for comparison to a silicon wafer by spin coating. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100℃for 5 minutes, and a uniform resin composition layer of about 15 μm thickness was obtained on the silicon wafer.
Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm 2 The entire surface of the obtained resin composition layer was subjected to i-ray exposure.
The resin composition layer (resin layer) after the exposure was heated at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere to a temperature described in the column "temperature" of "curing conditions" in the table, and then heated for 3 hours. The cured resin layer (cured film) was immersed in a 4.9 mass% aqueous hydrofluoric acid solution, and the cured film was peeled from the silicon wafer. The peeled cured film was punched out by a punching machine to prepare a test piece having a sample width of 3mm and a sample length of 30 mm. The elongation at break of the obtained test piece in the longitudinal direction was measured in accordance with JIS-K6251 in an environment of 25℃and 65% RH (relative humidity) at a crosshead speed of 300 mm/min by a tensile Tester (TENSILON). Each of the evaluations was performed 5 times, and the arithmetic average value of the elongation at break (elongation at break) of the test piece was used as an index value.
The index values were evaluated according to the following evaluation criteria, and the evaluation results are shown in the column of "elongation at break" in the table. It can be said that the greater the index value, the more excellent the film strength (elongation at break) of the obtained cured film.
(evaluation criterion)
A: the index value is 60% or more.
B: the index value is 55% or more and less than 60%.
C: the index value is 50% or more and less than 55%.
D: the index value is less than 50%.
[ evaluation of drug resistance ]
The resin compositions prepared in each of the examples and comparative examples or the comparative composition was applied to a silicon wafer by spin coating, respectively, to thereby form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100℃for 5 minutes, and a uniform resin composition layer of about 15 μm in thickness was formed on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm 2 The entire surface of the resin composition layer on the silicon wafer was exposed to light, the exposed resin composition layer (resin layer) was heated at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere, and the resin composition layer was heated at a temperature described in the column "temperature" of "curing conditions" in the table for 180 minutes, thereby obtaining a cured layer (resin layer) of the resin composition layer.
The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Liquid medicine: mixture of dimethyl sulfoxide (DMSO) and 25% by mass of tetramethylammonium hydroxide (TMAH) in water at a ratio of 90:10 (mass ratio)
Evaluation conditions: the resin layer was immersed in the chemical solution at 75℃for 15 minutes, and the film thicknesses before and after immersion were compared to calculate the dissolution rate (nm/min). Film thickness was measured on the coated surface 10 by ellipsometry (KT-22, manufactured by Foothill Co., ltd.) and the arithmetic average value was obtained as the film thickness.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "chemical resistance" in the table. It can be said that the slower the dissolution rate, the more excellent the chemical resistance.
Evaluation criterion-
A: the dissolution rate is less than 200 nm/min.
B: the dissolution rate is 200 nm/min or more and less than 300 nm/min.
C: the dissolution rate is 300 nm/min or more and less than 400 nm/min.
D: the dissolution rate is 400 nm/min or more.
[ evaluation of internal stress ]
The evaluation of the internal stress was performed as follows.
The resin compositions prepared in each example and comparative example, or the comparative composition, were applied to a 12-inch silicon wafer by spin coating, respectively, to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100℃for 5 minutes, and a uniform resin composition layer of about 15 μm in thickness was formed on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm 2 The entire surface of the resin composition layer on the silicon wafer was exposed to light, the exposed resin composition layer (resin layer) was heated at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere, and the resin composition layer was heated at a temperature described in the column "temperature" of "curing conditions" in the table for 180 minutes, thereby obtaining a cured layer (resin layer) of the resin composition layer. After the 180-minute heating step was completed for 24 hours, the warpage amount of the wafer was measured, and the internal stress was calculated according to the following formula.
Radius of curvature ρ=length of substrate L 2 /8ξ+ξ/2
L: length of substrate (12 inches, 1 inch = 2.54 cm)
ζ: amount of warpage
Internal stress=e 1 ×h 1 3 /12h 2 ×2/ρ(h 1 +h 2 )×[1+1/3{h 1 /(h 1 +h 2 )} 2 ]
E 1 : elastic modulus of substrate (MPa)
h 1 : thickness of substrate (775 μm)
h 2 : thickness of cured film after curing (measured by ellipsometer)
By JIS (Japanese Industrial Standard: japanese Industrial Standard) K7171: the method described in 2016 calculates the elastic modulus of a substrate.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "internal stress" in the table. It can be said that the smaller the internal stress is, the smaller and excellent the warpage of the wafer is.
Evaluation criterion-
A: the internal stress is less than 20mPa.
B: the internal stress is 20mPa or more and less than 25mPa.
C: the internal stress is 25mPa or more and less than 30mPa.
D: the internal stress is 30mP or more.
From the above results, it was found that the cured film formed from the resin composition of the present invention was excellent in drug resistance.
The comparative compositions of comparative examples 1 to 3 did not contain compound B.
The cured film formed from the comparative composition was found to have poor chemical resistance.
< example 101>
The resin composition used in example 1 was applied to the copper thin layer surface of the resin substrate having a copper thin layer formed thereon in a layer form by spin coating, dried at 100℃for 4 minutes to form a resin composition layer having a film thickness of 20. Mu.m, and then exposed to light by a stepper (manufactured by Nikon Corporation, NSR1505 i 6). Exposure was performed at 365nm wavelength through a mask (binary mask with a pattern of 1:1 lines and spaces, line width of 10 μm). After exposure, the layer was patterned by developing with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds.
Then, the temperature was raised at a temperature raising rate of 10 ℃/min under a nitrogen atmosphere, and after reaching 230 ℃, the temperature was maintained at 230 ℃ for 3 hours, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer is excellent in insulation properties.
Further, a semiconductor device was manufactured using the interlayer insulating film for a rewiring layer, and as a result, normal operation was confirmed.

Claims (16)

1. A resin composition comprising:
resin: which is a cyclized resin or precursor thereof; a kind of electronic device with high-pressure air-conditioning system
A compound B represented by the formula (1-1),
X 1 represents an n-valent linking group comprising an aromatic ring structure, X 1 At least 1 of the bonding sites with the nitrogen atom in the formula is an aromatic ring structure, R 1 Each independently represents a hydrogen atom or a 1-valent organic group, R 1 Optionally with X 1 Bonding to form a ring structure, Y 1 Each independently represents an m+1 valent linking group, W 1 Each independently represents a group containing a polymerizable group, n represents an integer of 1 or more, and m represents an integer of 1 or more.
2. The resin composition according to claim 1, wherein,
the content of the compound B is 1 mass% or more relative to the total mass of the resin composition.
3. The resin composition according to claim 1 or 2, further comprising a polymerizable compound different from the compound B.
4. The resin composition according to claim 3, wherein,
the content of the polymerizable compound is more than 0% by mass and 20% by mass or less relative to the total mass of the composition.
5. The resin composition according to any one of claim 1 to 4, wherein,
the acid value of the resin is less than 1 mmol/g.
6. The resin composition according to any one of claims 1 to 5, wherein,
the resin has a polymerizable group.
7. The resin composition according to any one of claims 1 to 6, wherein,
the molecular weight of the compound B is below 1000.
8. The resin composition according to any one of claims 1 to 7, further comprising a polymerization initiator.
9. The resin composition according to any one of claims 1 to 8, wherein,
w in the formula (1-1) 1 Is a radical polymerizable group.
10. The resin composition according to any one of claims 1 to 9, which is used for forming an interlayer insulating film for a rewiring layer.
11. A cured product obtained by curing the resin composition according to any one of claims 1 to 10.
12. A laminate comprising 2 or more layers formed of the cured product of claim 11, wherein any layers formed of the cured product contain a metal layer between each other.
13. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 10 to a substrate to form a film.
14. The method for producing a cured product according to claim 13, comprising an exposure step of exposing the film and a development step of developing the film.
15. The method for producing a cured product according to claim 13 or 14, comprising a heating step of heating the film at 50 to 450 ℃.
16. A semiconductor device comprising the cured product of claim 11 or the laminate of claim 12.
CN202280025200.5A 2021-03-30 2022-03-24 Resin composition, cured product, laminate, method for producing cured product, and semiconductor device Pending CN117083346A (en)

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