CN113614130B - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device Download PDF

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Publication number
CN113614130B
CN113614130B CN202080022620.9A CN202080022620A CN113614130B CN 113614130 B CN113614130 B CN 113614130B CN 202080022620 A CN202080022620 A CN 202080022620A CN 113614130 B CN113614130 B CN 113614130B
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group
resin composition
curable resin
formula
polymerizable compound
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CN113614130A (en
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井上遥菜
青岛俊荣
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • B32B15/088—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 comprising polyamides
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/20—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
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Graft Or Block Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

The present invention provides a curable resin composition comprising at least 1 polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and a polymerizable compound having a hydrogen bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups, wherein the free radical polymerizable group valence of the compound derived from a compound having a free radical polymerizable group having a molecular weight of 2,000 or less is 0.25 to 4.35mmol/g relative to the total solid content of the composition, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.

Description

Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
Technical Field
The invention relates to a curable resin composition, a cured film, a laminate, a method for producing the cured film, and a semiconductor device.
Background
A resin obtained by cyclizing and curing a polymer precursor such as a polyimide resin or a polybenzoxazole resin (hereinafter, a polyimide resin precursor and a polybenzoxazole resin precursor are also collectively referred to as a "heterocyclic polymer-containing precursor") is excellent in heat resistance and insulation properties, and thus can be suitably used for various applications. The above-mentioned applications are not particularly limited, but when a semiconductor device for actual mounting is taken as an example, use of a material or a protective film as an insulating film or a sealing material can be exemplified. And also as a base film, a cover film, or the like of a flexible substrate.
For example, in the above-mentioned applications, the heterocyclic polymer-containing precursor is used in the form of a curable resin composition containing the heterocyclic polymer-containing precursor. Such a curable resin composition can be applied to a substrate, for example, by coating, and then the heterocyclic polymer-containing precursor can be cyclized by heating or the like to form a cured resin on the substrate. Since the curable resin composition can be applied by a known coating method or the like, it can be said that the curable resin composition to be applied has high flexibility in manufacturing such as a high degree of freedom in design such as shape, size, and application position. In addition to the high performance of polyimide resins and the like, from the viewpoint of excellent suitability for production, there is an increasing demand for expansion of industrial applications of curable resin compositions containing heterocyclic polymer precursors.
For example, patent document 1 describes a photosensitive resin composition containing a polyimide precursor, at least 1 polyimide resin, and at least 1 urethane (meth) acrylate having a specific structure.
Technical literature of the prior art
Patent literature
Patent document 1: international publication No. 2017/131037
Disclosure of Invention
Technical problem to be solved by the invention
In the formation of a cured film obtained by curing a curable resin composition containing a heterocyclic polymer precursor such as a polyimide precursor, for example, when a laminate is produced by further applying and curing the curable resin composition to the cured film, the cured film may be brought into contact with a developer or other composition.
Accordingly, in the curable resin composition, for example, from the viewpoints of resistance to a developer, inhibition of dissolution due to contact with other compositions, and the like, it is desired to provide a curable resin composition excellent in the drug resistance of the obtained cured film.
Further, in a cured film obtained by curing a curable resin composition containing a heterocyclic polymer precursor, it is desired to provide a curable resin composition excellent in elongation at break.
The present invention provides a curable resin composition excellent in chemical resistance and elongation at break of a cured film obtained, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.
Means for solving the technical problems
An example of a representative embodiment of the present invention is shown below.
<1> A curable resin composition comprising:
A polymer precursor which is at least 1 selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and
A polymerizable compound having a hydrogen-bonding nitrogen atom and a group containing 2 or more ethylenically unsaturated groups,
The radical polymerizable group valence derived from a compound having a radical polymerizable group having a molecular weight of 2,000 or less is 0.25 to 4.35mmol/g with respect to the total solid content of the composition.
<2> The curable resin composition according to <1>, wherein the polymerizable compound has a structure A as a structure containing the hydrogen-bonding nitrogen atom, and the structure A is at least 1 structure selected from the group consisting of urethane bonds, urea bonds and amide bonds.
<3> The curable resin composition according to <2>, wherein the polymerizable compound comprises a structure B, and the structure B is a structure in which at least 1 bonding site in the structure A is directly bonded to an alkylene group.
< 4 > A curable resin composition comprising:
A polymer precursor which is at least 1 selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and
A polymerizable compound having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups.
The curable resin composition according to any one of < 5 > to <1> to < 4 >, wherein the polymerizable compound contains a (meth) acryloyl group as a group containing the ethylenically unsaturated group.
The curable resin composition according to any one of < 6 > to <1 > to < 5 >, wherein the polymerizable compound has a molecular weight of 200 to 1,000.
The curable resin composition according to any one of < 7 > to < 1 > to < 6 >, further comprising a photo radical polymerization initiator.
The curable resin composition according to any one of < 8 > to <1> to < 7 >, further comprising an onium salt or a thermoalcifer.
A curable resin composition according to any one of < 9 > to < 1 > to < 8 > comprising a polyimide precursor as the polymer precursor.
A curable resin composition according to the above-mentioned formula (1) wherein the polyimide precursor has a repeating unit represented by the following formula (10) < 9 >,
[ Chemical formula 1]
In formula (1), A 1 and A 2 each independently represent an oxygen atom or-NH-, R 111 represents a 2-valent organic group, R 115 represents a 4-valent organic group, and R 113 and R 114 each independently represent a hydrogen atom or a 1-valent organic group.
The curable resin composition according to claim 11 < 10, wherein at least 1 of R 113 and R 114 in the formula (1) contains a radical polymerizable group.
A curable resin composition according to any one of < 12 > to < 1 > to < 11 > for forming an interlayer insulating film for a re-wiring layer.
A curable film obtained by curing the curable resin composition of any one of < 1 > - < 12 >.
< 14 > A laminate comprising 2 or more layers of the cured film described as < 13 > and a metal layer between any of the cured films.
A method for producing a cured film, comprising a film formation step of applying the curable resin composition of any one of < 1 > - < 12 > to a substrate to form a film.
A method for producing a cured film according to claim 16 or 15, which comprises an exposure step of exposing the film and a development step of developing the film.
A method for producing a cured film according to claim 17, 15 or 16, which comprises a heating step of heating the film at 50 to 450 ℃.
< 18 > A semiconductor device comprising the cured film < 13> or the laminate < 14 >.
Effects of the invention
According to the present invention, there are provided a curable resin composition excellent in chemical resistance and elongation at break of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.
Detailed Description
Hereinafter, a main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiments.
In the present specification, a numerical range indicated by a symbol "to" indicates 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 not only an independent process but also a process which cannot be clearly distinguished from other processes as long as the desired function of the process can be achieved.
Regarding the labeling of groups (radicals) in the present specification, the unsubstituted and substituted labels include both groups (radicals) having no substituent and groups (radicals) 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, "exposure" includes, unless otherwise specified, exposure by a particle beam such as an electron beam or an ion beam, in addition to exposure by light. The light used for exposure includes an open line spectrum of a mercury lamp, and actinic rays or radiation such as extreme ultraviolet rays (EUV light), X-rays, and electron beams, which are typified by excimer laser light.
In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", "(meth) acrylic acid" means either or both of "acrylic acid" and "methacrylic acid", and "(meth) acryl" means either or both of "acryl" and "methacryl", 1 ".
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 component means the total mass of components of which the solvent is removed from the total 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 defined as polystyrene equivalent values based on gel permeation chromatography (GPC measurement). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using HLC-8230 GPC (TOSOH CORPORATION, manufactured by the following method) as a column, and using a protection column HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000(TOSOH CORPORATION, for example. These molecular weights are not particularly limited, and a solution measured using THF (tetrahydrofuran) is used as an eluent. Further, unless otherwise specified, a 254nm wavelength detector of UV rays (ultraviolet rays) was 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", another layer may be present above or below the layer to be 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 layers, and the layer to be the reference may not be in contact with the other layers. The direction of stacking the layers on the substrate is referred to as "up", or the direction from the substrate toward the photosensitive layer is referred to as "up", and the opposite direction is referred to as "down", unless otherwise specified. In addition, these vertical directions may be set for convenience in the present specification, and in actual embodiments, the "upward" direction in the present specification may be oriented differently from the vertical direction.
In this 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 indicates the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, physical properties are values under conditions of a temperature of 23℃and a gas pressure of 101, 325Pa (1 gas pressure).
In this specification, a combination of preferred embodiments is a more preferred embodiment.
(Curable resin composition)
In the first aspect of the curable resin composition of the present invention, the curable resin composition contains at least 1 polymer precursor (heterocyclic polymer-containing precursor) selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a polymerizable compound having a hydrogen bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups (hereinafter, also referred to as "specific polymerizable compound 1"), and the radical polymerizable group valence of the compound having a radical polymerizable group derived from a compound having a molecular weight of 2,000 or less is 0.25 to 4.35mmol/g with respect to the total solid content of the composition.
In a second aspect of the curable resin composition of the present invention, the curable resin composition contains at least 1 polymer precursor (heterocyclic polymer-containing precursor) selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a polymerizable compound having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups (hereinafter, also referred to as "specific polymerizable compound 2").
Hereinafter, the curable resin compositions according to the first and second aspects of the curable resin composition of the present invention are also simply referred to as "curable resin composition", and the specific polymerizable compound 1 and the specific polymerizable compound 2 are simply referred to as "specific polymerizable compound".
The curable resin composition of the present invention preferably further comprises a photo radical polymerization initiator described later.
The cured film obtained from the curable resin composition of the present invention is excellent in chemical resistance and elongation at break.
The mechanism for obtaining the above effects is not clear, but it is presumed as follows.
For example, when a curable resin composition containing a heterocyclic polymer precursor is heated, a cured film containing a polyimide resin or a polybenzoxazole resin can be obtained by cyclization of the precursor.
Among them, in order to improve the chemical resistance of the cured film, it is considered to further introduce a compound having an ethylenically unsaturated group.
However, as a result of intensive studies by the present inventors, it has been found that when a radical polymerizable group derived from a compound having a radical polymerizable group having a molecular weight of 2,000 or less relative to the total solid content of the composition has a high valence (for example, more than 4.35 mmol/g), and the like, in the case of using a conventional ethylenically unsaturated compound, for example, in curing at a low temperature of 200 ℃ or less, cyclization of the heterocyclic polymer precursor is suppressed, and the resulting cured film has improved chemical resistance but reduced elongation at break.
In this way, it is difficult to achieve both drug resistance and elongation at break in the cured film obtained.
Accordingly, the present inventors have found that a cured film excellent in chemical resistance and elongation at break can be obtained by using a specific polymerizable compound 1 having a hydrogen bonding nitrogen atom and a double bond in a composition and setting the radical polymerizable group to a valence of 0.25 to 4.35mmol/g or using a specific polymerizable compound 2 having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups.
This is presumably because a strong film is formed by hydrogen bonding between specific polymerizable compounds after crosslinking or between specific polymerizable compounds after crosslinking and polyimide resin, polybenzoxazole resin or the like.
Further, it is considered that the curable resin composition of the present invention is also easily excellent in lithography property by using the above-mentioned specific polymerizable compound 2 having a radical polymerizable group valence of 0.25mol/g or more or having a urea bond or an amide bond.
In patent document 1, there is no description or suggestion of a curable resin composition containing a specific polymerizable compound 1 and having a radical polymerizable group valence of 0.25 to 4.35mmol/g and a curable resin composition containing a specific polymerizable compound 2. In addition, in the curable resin composition of patent document 1, there is room for further improvement in the drug resistance of a cured film of the curable resin composition.
The components contained in the curable resin composition of the present invention will be described in detail below.
In the first and second aspects of the curable resin composition of the present invention, the components other than the specific polymerizable compound and the composition or physical properties other than the radical polymerizable group valence contained in the composition are the same, and the preferable aspects thereof are the same.
< Heterocyclic-containing Polymer precursor >
The curable resin composition of the present invention contains a heterocyclic polymer-containing precursor.
The curable resin composition of the present invention contains at least 1 precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, preferably contains a polyimide precursor, as the heterocyclic polymer precursor.
[ Polyimide precursor ]
From the viewpoint of film strength of the obtained cured film, the polyimide precursor preferably has a repeating unit represented by the following formula (1).
[ Chemical formula 2]
In formula (1), A 1 and A 2 each independently represent an oxygen atom or-NH-, R 111 represents a 2-valent organic group, R 115 represents a 4-valent organic group, and R 113 and R 114 each independently represent a hydrogen atom or a 1-valent organic group.
A 1 and A 2 -
A 1 and A 2 in the formula (1) each independently represent an oxygen atom or-NH-, preferably an oxygen atom.
-R111-
R 111 in the formula (1) represents a 2-valent organic group. Examples of the 2-valent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a combination of 2 or more groups, 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 combination of 2 or more groups, more preferably an aromatic group having 6 to 20 carbon atoms.
R 111 in formula (1) is preferably derived from a diamine. 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 preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a diamine in which these groups are combined with 2 or more groups, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.
[ Chemical formula 3]
In the formula, A is preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=O) -, -S (=O) 2 -, -NHC (=O) -, or a combination of 2 or more groups, more preferably a single bond, a group selected from the group consisting of an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-and S (=O) 2 -, and still more preferably a 2-valent group selected from the group consisting of-CH 2-、-O-、-S-、-S(＝O)2-、-C(CF3)2 -and-C (CH 3)2 -.
Specific examples of the diamine include a diamine selected from 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-diaminocyclopentane or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane or 1, 4-diaminocyclohexane, 1, 2-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane or isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4' -diaminobiphenyl or 3,3' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -diaminodiphenylmethane or 3,3' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone or 3,3' -diaminodiphenylsulfone 4,4' -diaminodiphenyl sulfide or 3,3' -diaminodiphenyl sulfide, 4' -diaminobenzophenone or 3,3' -diaminobenzophenone, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl (4, 4' -diamino-2, 2' -dimethylbiphenyl), and 3,3' -dimethoxy-4, 4' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -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' -diaminodiphenylmethane, 3' -dimethyl-4, 4' -diaminodiphenylmethane, 4' -diaminooctafluorobiphenyl 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydro-anthracene, 3',4,4' -tetraminobiphenyl, 3',4,4' -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',5,5' -tetramethyl-4, 4' -diaminodiphenylmethane, 2- (3 ', ethyl 5 '-diaminobenzoyloxy) methacrylate, 2, 4-diaminocumene or 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecahydroheptane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4 '-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4 '-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3', at least 1 diamine selected from the group consisting of 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) shown below are also preferable.
[ Chemical formula 4]
[ Chemical formula 5]
Further, as a preferable example, a diamine having at least 2 alkylene glycol units in the main chain can be given. It is preferable to combine a diamine containing any one of 2 or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferable is a diamine containing no aromatic ring. Specific examples thereof include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN corporation), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (2-aminopropoxy) propane-2-yl) oxy) propane-2-amine, and the like, but are not limited thereto.
The structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176 are shown below.
[ Chemical formula 6]
In the above, x, y and z are arithmetic mean values.
From the viewpoint of flexibility of the resulting cured film, R 111 in the formula (1) is preferably represented by-Ar 0-L0-Ar0 -. Ar 0 is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L 0 represents a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=O) -, -S (=O) 2 -, -NHCO-, or a combination of 2 or more of these groups. The preferred range of L 0 has the same meaning as A above.
From the viewpoint of the i-ray transmittance, R 111 in the formula (1) is preferably a 2-valent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of the i-ray transmittance and availability, the 2-valent organic group represented by the formula (61) is more preferable.
[ Chemical formula 7]
In formula (51), R 50～R57 is each independently a hydrogen atom, a fluorine atom, or a 1-valent organic group, and at least 1 of R 50～R57 is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group, each independently represents a bonding site to another structure.
Examples of the 1-valent organic group of R 50～R57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.
[ Chemical formula 8]
In formula (61), R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.
Examples of the diamine compound having a structure represented by the formula (51) or (61) include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4,4' -diaminooctafluorobiphenyl. 1 of these may be used, or 2 or more may be used in combination.
-R115-
R 115 in the formula (1) 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).
[ Chemical formula 9]
R 112 has the same meaning as A, and the preferred ranges are also the same. * Each independently represents a bonding site with another structure.
Specific examples of the 4-valent organic group represented by R 115 in the formula (1) include a tetracarboxylic acid residue remaining after removal of an acid dianhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used in an amount of 1 or 2 or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
[ Chemical formula 10]
R 115 represents a 4-valent organic group. R 115 has the same meaning as R 115 of formula (1).
Specific examples of the tetracarboxylic dianhydride include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride, 3',4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -diphenylmethane tetracarboxylic dianhydride, 2',3,3' -diphenylmethane tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 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, and 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-perylenetetracarboxylic 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-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, and at least 1 of alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms of these.
Further, preferred examples thereof include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.
[ Chemical formula 11]
R 113 and R 114 -
R 113 and R 114 in the formula (1) each independently represent a hydrogen atom or a 1-valent organic group. Preferably, at least 1 of R 113 and R 114 contains a radically polymerizable group, more preferably both contain a radically polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a group containing an ethylenic unsaturated bond is preferable.
Examples of the group containing an ethylenic unsaturated bond include a vinyl group, an allyl group, a (meth) acryl group, a group represented by the following formula (III), and the like.
[ Chemical formula 12]
In formula (III), R 200 represents a hydrogen atom or a methyl group, preferably a methyl group.
In the formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2CH(OH)CH2 -, or a (poly) oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3, and the number of repetition is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3). Further, (poly) oxyalkylene means oxyalkylene or polyoxyalkylene.
Examples of preferable R 201 include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH 2CH(OH)CH2 -, and more preferably ethylene, propylene, trimethylene, -CH 2CH(OH)CH2 -.
Particularly preferably, R 200 is methyl and R 201 is ethylene.
In formula (III), the bonding sites to other structures are represented.
In a preferred embodiment of the polyimide precursor of the present invention, examples of the 1-valent organic group of R 113 or R 114 include an aliphatic group, an aromatic group, an aralkyl group, and the like having 1,2, or 3 acid groups, preferably 1 acid group. Specifically, examples thereof include an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group are exemplified. The acid group is preferably a hydroxyl group. That is, R 113 or R 114 is preferably a group having a hydroxyl group.
As the 1-valent organic group represented by R 113 or R 114, a substituent that improves the solubility of the developer may be preferably used.
R 113 or R 114 is more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group from the viewpoint of solubility in an aqueous developer.
From the viewpoint of solubility in an organic solvent, R 113 or R 114 is preferably a 1-valent organic group. The 1-valent organic group is preferably a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more when cyclic). The alkyl group may be any of linear, branched, and cyclic. Examples of the straight-chain or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl and 2-ethylhexyl groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, bornyl, camphene (camphenyl), decalin, tricyclodecyl, tetracyclodecyl, camphan diacyl, dicyclohexyl and pinenyl (pinenyl). The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group described below.
The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (as a cyclic structure constituting a group, examples thereof include benzene ring, naphthalene ring, biphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, heptene ring, and the like indene ring, perylene ring, pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, tetracene ring,Ring, triphenylene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (as a cyclic structure constituting a group, a fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, benzopyran ring, xanthene ring, phenoxathiazide ring, phenothiazine ring, or phenazine ring).
In addition, the polyimide precursor preferably has a fluorine atom in the repeating unit. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, more preferably 20 mass% or more. The upper limit is not particularly limited, but is practically 50 mass% or less.
In order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the repeating unit represented by formula (1). Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A) or the formula (1-B).
[ Chemical formula 13]
A 11 and A 12 represent an oxygen atom or-NH-, R 111 and R 112 each independently represent a 2-valent organic group, R 113 and R 114 each independently represent a hydrogen atom or a 1-valent organic group, at least one of R 113 and R 114 is preferably a group containing a radical polymerizable group, more preferably a radical polymerizable group.
The preferred ranges of A 11、A12、R111、R113 and R 114 have the same meanings as those of A 1、A2、R111、R113 and R 114 in formula (1), respectively.
The preferred range of R 112 has the same meaning as R 112 in formula (5), wherein an oxygen atom is more preferred.
In the formula (A), the bonding position of carbonyl group on benzene ring is preferably 4,5, 3', 4' in the formula (1-A). In the formula (1-B), 1,2,4, 5 are preferable.
In the polyimide precursor, the number of the repeating units represented by the formula (1) may be 1 or 2 or more. And, structural isomers of the repeating unit represented by formula (1) may be included. In addition to the repeating unit of the above formula (1), the polyimide precursor may contain other types of repeating units.
As an embodiment of the polyimide precursor of the present invention, a polyimide precursor in which 50 mol% or more, more preferably 70 mol% or more, and particularly 90 mol% or more of the repeating units represented by formula (1) are total repeating units can be exemplified. The upper limit is practically 100 mol% or less.
The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 ～ 500,000, more preferably 5,000 ～ 100,000, and further 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 dispersity of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the dispersity of the molecular weight means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).
The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the acid is obtained by halogenating a dicarboxylic acid or dicarboxylic acid derivative with a halogenating agent and then reacting the resultant with a diamine.
In the method for producing a polyimide precursor, an organic solvent is preferably used in the reaction. The organic solvent may be 1 or 2 or more.
The organic solvent may be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone may be exemplified.
In the case of producing a polyimide precursor, it is preferable to include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction liquid is precipitated in water and dissolved in a solvent in which the polyimide precursor such as tetrahydrofuran is soluble, whereby solid precipitation can be performed.
[ Polybenzoxazole precursors ]
The polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).
[ Chemical formula 14]
In formula (2), R 121 represents a 2-valent organic group, R 122 represents a 4-valent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a 1-valent organic group.
-R121-
In formula (2), R 121 represents a 2-valent organic group. The 2-valent organic group is preferably a group containing at least 1 of an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 12 carbon atoms). Examples of the aromatic group constituting R 121 include R 111 of the above formula (1). The aliphatic group is preferably a linear aliphatic group. R 121 is preferably derived from 4,4' -oxo-dibenzoyl chloride.
-R122-
In formula (2), R 122 represents a 4-valent organic group. The meaning of the 4-valent organic group is the same as R 115 in the above formula (1), and the preferable range is also the same. R 122 is preferably derived from 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R 123 and R 124 -
R 123 and R 124 each independently represent a hydrogen atom or a 1-valent organic group, and the meanings are the same as those of R 113 and R 114 in the above formula (1), and the preferable ranges are also the same.
In addition to the repeating units of formula (2) above, the polybenzoxazole precursor may also contain other kinds of repeating units.
From the viewpoint of being able to suppress warpage of a cured film accompanying ring closure, the polybenzoxazole precursor preferably further contains a diamine residue represented by the following formula (SL) as another kind of repeating unit.
[ Chemical formula 15]
Z has a structure of a and a structure of b, R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R 2s is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), at least 1 of R 3s、R4s、R5s、R6s is an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms), and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) and may be the same or different. The polymerization of the a and b structures may be block polymerization or random polymerization. In the Z moiety, the a structure is preferably 5 to 95 mol%, the b structure is preferably 95 to 5 mol%, and the a+b is preferably 100 mol%.
In the formula (SL), preferable Z is that R 5s and R 6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography which is generally used. By setting the molecular weight in the above range, the effect of reducing the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and the effect of suppressing warpage and the effect of improving solubility can be achieved.
When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another type of repeating unit, it is further preferable to contain a tetracarboxylic acid residue remaining after removal of an acid dianhydride group from a tetracarboxylic acid dianhydride as a repeating unit in view of improving the alkali solubility of the curable resin composition. Examples of such tetracarboxylic acid residues include R 115 in formula (1).
The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 ～ 500,000, more preferably 5,000 ～ 100,000, further 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 dispersity of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
The content of the heterocyclic polymer-containing precursor in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and still more preferably 70% by mass or more, based on the total solid content of the curable resin composition. The content of the heterocyclic polymer-containing precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, still further preferably 97% by mass or less, and still further preferably 95% by mass or less, based on the total solid content of the curable resin composition.
The curable resin composition of the present invention may contain only 1 kind of heterocyclic polymer precursor or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
< Specific polymerizable Compound 1>
In the first aspect of the curable resin composition of the present invention, the composition comprises a polymerizable compound having a hydrogen bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups (specific polymerizable compound 1), and the free radical polymerizable group valence of the compound having a free radical polymerizable group having a molecular weight of 2,000 or less is 0.25 to 4.35mmol/g with respect to the total solid content of the composition.
[ Valence of radical polymerizable group ]
The radical polymerizable group valence of the radical polymerizable group-containing compound having a molecular weight of 2,000 or less with respect to the total solid content of the composition refers to the amount (mol amount) of the ethylenic unsaturated group contained in the radical polymerizable group-containing compound having a molecular weight of 2,000 or less with respect to the total solid content of the composition.
The valence of the radical polymerizable group can be determined based on the structure determination based on the separation of a compound having a radical polymerizable group having a molecular weight of 2,000 or less and the concentration measurement in a composition based on chromatography or the like.
The valence of the radical polymerizable group is preferably 0.25 to 4.35mmol/g, more preferably 0.50 to 3.50mol/g.
[ Ethylenically unsaturated group ]
Examples of the ethylenically unsaturated group contained in the specific polymerizable compound 1 include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryl group, and the like, preferably a (meth) acryl group, and more preferably a (meth) acryloyloxy group from the viewpoint of reactivity.
The number of ethylenic unsaturation in the specific polymerizable compound 1 is not less than 2, more preferably 2 to 8, and still more preferably 2 to 6.
The molar amount (mol/g) of the ethylenically unsaturated group in 1g of the specific polymerizable compound 1 is preferably 0.004 to 0.015mol/g, more preferably 0.005 to 0.012mol/g.
[ Hydrogen bonding Nitrogen atom ]
The hydrogen bonding nitrogen atom contained in the specific polymerizable compound 1 is not particularly limited, and examples thereof include nitrogen atoms contained in urethane bonds (-o—c (=o) -NR N -), urea bonds (-NR N-C(＝O)-NRN -), amide bonds (-C (=o) -NR N -), amino groups (-NR N -), sulfonamide bonds (-S (=o) 2NRN -), nitrogen-containing heterocyclic structures, and the like. R N represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and still more preferably a hydrogen atom. When a plurality of R N exist in a molecule, a plurality of R N may be the same or different.
The specific polymerizable compound 1 preferably contains, as a structure containing a hydrogen-bonding nitrogen atom, a structure a of at least 1 selected from the group consisting of a urethane bond, a urea bond, and an amide bond.
In addition, from the viewpoint of improving the elongation at break, the specific polymerizable compound 1 preferably contains a urethane bond as a structure containing a hydrogen-bonding nitrogen atom, and from the viewpoint of improving the drug resistance, the specific polymerizable compound 1 preferably contains at least 1 structure selected from the group consisting of urea bonds and amide bonds as a structure containing a hydrogen-bonding nitrogen atom.
The number of hydrogen-bonding nitrogen atoms in the specific polymerizable compound 1 is preferably 2 to 6, more preferably 2 to 4.
The specific polymerizable compound 1 preferably includes a structure B in which at least 1 bonding site in the structure a is directly bonded to an alkylene group.
The alkylene group is preferably an alkylene group having 2 to 15 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms. The alkylene group may be an alkylene group having a branched structure or a cyclic structure.
[ Specific polymerizable Compound 1 containing urethane bond ]
The specific polymerizable compound 1 containing a urethane bond is preferably a compound represented by the following formula (UA-1) or formula (UA-2).
[ Chemical formula 16]
In the formula (UA-1) or (UA-2), L A1 represents a linker having a valence of nA, L A2 each independently represents a linker having a valence of mA+1, R A1 each independently represents a group containing an ethylenically unsaturated group, nA represents an integer of 2 or more, and mA represents an integer of 1 or more.
In the formula (UA-1) or (UA-2), L A1 is preferably a nA-valent hydrocarbon group, more preferably a nA-valent aliphatic saturated hydrocarbon group, a nA-valent aromatic hydrocarbon group, or a nA-valent group represented by a combination of an aliphatic saturated hydrocarbon group and an aromatic hydrocarbon group.
In the formula (UA-1) or (UA-2), L A2 is preferably a hydrocarbon group, an ester bond (—c (=o) O-), an ether bond (—o-), a carbonyl group (—c (=o) -), a urethane bond (—o—c (=o) -NR N -), a urea bond (—nr N-C(＝O)-NRN -), an amide bond (—c (=o) -NR N -), an amino group (—nr N -), or a group in which 2 or more of these are combined, more preferably an aliphatic saturated hydrocarbon group, an aromatic hydrocarbon group, an ester bond, an ether bond, or a group in which 2 or more of these are combined. R N is as described above.
In the formula (UA-1) or the formula (UA-2), R A1 is preferably vinyl, allyl, vinylphenyl, (meth) acrylamido or (meth) acryloyloxy, more preferably (meth) acryloyloxy.
In the formula (UA-1) or (UA-2), nA represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 2.
In the formula (UA-1) or the formula (UA-2), mA is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1.
[ Specific polymerizable Compound 1 comprising a Urea bond ]
The specific polymerizable compound 1 containing a urea bond is preferably a compound represented by the following formula (UB-1).
[ Chemical formula 17]
In the formula (UB-1), L B1 represents a linking group having a valence of nB, L B2 each independently represents a linking group having a valence of mB+1, R B1 each independently represents a group containing an ethylenically unsaturated group, nB represents an integer of 2 or more, and mB represents an integer of 1 or more.
In the formula (UB-1), L B1 is preferably an nB-valent hydrocarbon group, more preferably an nB-valent aliphatic saturated hydrocarbon group, an nB-valent aromatic hydrocarbon group, or an nB-valent group represented by a combination of an aliphatic saturated hydrocarbon group and an aromatic hydrocarbon group.
In the formula (UB-1), L B2 is preferably a hydrocarbon group, an ester bond (-C (=o) O-, ether bond (-O-), carbonyl group (-C (=o) -), a urethane bond (-O-C (=o) -NR N -), a urea bond (-NR N-C(＝O)-NRN -), an amide bond (-C (=o) -NR N -), an amino group (-NR N -) or a group combining 2 or more of these, more preferably an aliphatic saturated hydrocarbon group, an aromatic hydrocarbon group, an ester bond, an ether bond or a group combining 2 or more of these. R N is as described above.
In the formula (UB-1), R B1 is preferably vinyl, allyl, vinylphenyl, (meth) acrylamido or (meth) acryloyloxy, more preferably (meth) acryloyloxy.
In the formula (UB-1), nB represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 2.
In the formula (UB-1), mB is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1.
[ Specific polymerizable Compound 1 containing an amide bond ]
The specific polymerizable compound 1 containing an amide bond preferably contains 2 or more structures represented by the following formula (AM-1) and 2 structures represented by the following formula (AM-2) in total.
[ Chemical formula 18]
In the formula (AM-1) and the formula (AM-2), R M1 represents a hydrogen atom or a methyl group, R M2 represents a hydrogen atom or a hydrocarbon group, and each independently represents a bonding site to other structures.
In the formula (AM-1) and the formula (AM-2), R M1 is preferably a hydrogen atom.
In the formula (AM-1), R M2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, further preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.
The specific polymerizable compound 1 containing an amide group is preferably a compound represented by the following formula (AM-3).
[ Chemical formula 19]
In the formula (AM-3), R M1 represents a hydrogen atom or a methyl group, R M2 represents a hydrogen atom or a hydrocarbon group, L M1 represents an n+1-valent organic group, n represents an integer of 1 or more, and when n is 1, L M1 has a group containing an ethylenically unsaturated group.
In the formula (AM-3), R M1 is preferably a hydrogen atom.
In the formula (AM-3), R M2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, further preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.
In the formula (AM-3), L M1 represents an n-valent organic group, preferably a hydrocarbon group, an ester bond (—c (=o) O-, ether bond (—o), carbonyl group (—c (=o) -), a urethane bond (—o—c (=o) -NR N -, urea bond (—nr N-C(＝O)-NRN -, C (=o) -NR N -, etc.), an amino group (—nr N), a structure represented by the above formula (AM-2), or a group combining 2 or more of these, more preferably an aliphatic saturated hydrocarbon group, an aromatic hydrocarbon group, an ester bond, an ether bond, a structure represented by the above formula (AM-2), or a group combining 2 or more of these. R N is as described above.
N is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 4.
When n is 1, L M1 has a group containing an ethylenically unsaturated group, and preferably contains a structure represented by the above formula (AM-2).
Further, from the viewpoint of further improving the elongation at break of the obtained cured film, the specific polymerizable compound 1 containing an amide group is also preferably a compound represented by the following formula (AM-4) or formula (AM-5).
[ Chemical formula 20]
In the formula (AM-4) or (AM-5), L B1 represents a linking group having a valence of nB, L B2 each independently represents a linking group having a valence of mB+1, R B1 each independently represents a group containing an ethylenically unsaturated group, nB represents an integer of 2 or more, and mB represents an integer of 1 or more.
In the formula (AM-4) or (AM-5), L B1 is preferably an nB-valent hydrocarbon group, more preferably an nB-valent aliphatic saturated hydrocarbon group, an nB-valent aromatic hydrocarbon group, or an nB-valent group represented by a combination of an aliphatic saturated hydrocarbon group and an aromatic hydrocarbon group.
In the formula (AM-4) or (AM-5), L B2 is preferably a hydrocarbon group, an ester bond (—c (=o) O-), an ether bond (—o-), a carbonyl group (—c (=o) -), a urethane bond (—o—c (=o) -NR N -), a urea bond (—nr N-C(＝O)-NRN -), an amide bond (—c (=o) -NR N -), an amino group (—nr N -), or a group in which 2 or more of these are combined, more preferably an aliphatic saturated hydrocarbon group, an aromatic hydrocarbon group, an ester bond, an ether bond, or a group in which 2 or more of these are combined. R N is as described above.
In the formula (AM-4) or (AM-5), R B1 is preferably vinyl, allyl, vinylphenyl, (meth) acrylamido or (meth) acryloyloxy, more preferably (meth) acryloyloxy.
In the formula (AM-4) or (AM-5), nB represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, particularly preferably 2 or 3.
In the formula (AM-4) or (AM-5), mB is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1.
[ Molecular weight ]
The molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific polymerizable compound 1 is preferably 200 to 1,000, more preferably 260 to 800, and still more preferably 265 to 765.
[ Specific example ]
Specific examples of the specific polymerizable compound 1 include, but are not limited to, compounds having the following structures.
[ Chemical formula 21]
[ Chemical formula 22]
[ Synthetic method ]
The method for synthesizing the specific polymerizable compound 1 is not particularly limited, and may be synthesized by a known method.
The specific polymerizable compound 1 containing a urethane bond can be obtained, for example, by reacting a polyisocyanate compound with a compound having a hydroxyl group and an ethylenically unsaturated group. Further, as another synthesis method, for example, it can be obtained by reacting a polyol compound with a compound having an isocyanate group and an ethylenically unsaturated group.
The specific polymerizable compound 1 containing a urea bond can be obtained, for example, by reacting a polyvalent isocyanate compound with a compound having an amino group and an ethylenically unsaturated group.
The specific polymerizable compound 1 containing an amide bond can be obtained, for example, by reacting a polyamine compound with an unsaturated carboxylic acid compound. Further, as another synthesis method, for example, it can be obtained by reacting a compound having an amino group and an ethylenically unsaturated group with a polycarboxylic acid halide compound.
Further, as the specific polymerizable compound 1, a commercially available compound may be used.
[ Content ]
The content of the specific polymerizable compound 1 is preferably more than 0% by mass and 60% by mass or less relative to the total solid content of the composition in the first embodiment of the curable 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 specific polymerizable compound 1 may be used alone or in combination of at least 2. When 2 or more kinds are used simultaneously, the total amount thereof is preferably within the above range.
< Specific polymerizable Compound 2 >
In a second aspect of the curable resin composition of the present invention, the composition includes a polymerizable compound (specific polymerizable compound 2) having a urea bond or an amide bond and having a group containing 2 or more ethylenically unsaturated groups.
[ Ethylenically unsaturated group ]
Examples of the ethylenically unsaturated group contained in the specific polymerizable compound 2 include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryl group, and the like, preferably a (meth) acryl group, and more preferably a (meth) acryloyloxy group from the viewpoint of reactivity.
The number of ethylenic unsaturation in the specific polymerizable compound 2 is not less than 2, more preferably 2 to 8, and still more preferably 2 to 6.
The molar amount (mol/g) of the ethylenically unsaturated group in 1g of the specific polymerizable compound 2 is preferably 0.004 to 0.015mol/g, more preferably 0.005 to 0.012mol/g.
[ Urea bond or amide bond ]
When the specific polymerizable compound 2 contains a urea bond (-NR N-C(＝O)-NRN), the number of urea bonds in the specific polymerizable compound 2 is preferably 1 to 10, more preferably 2 to 6, and still more preferably 2 to 4.R N is as described above.
When the specific polymerizable compound 2 contains an amide bond (-NR N -C (=o) -) the number of amide bonds in the specific polymerizable compound 2 is preferably 1 to 10, more preferably 2 to 6, still more preferably 2 to 4.R N is as described above.
The specific polymerizable compound 2 containing a urea bond is the same as the specific polymerizable compound 1 containing a urea bond, and the preferable mode and specific examples are the same.
The specific polymerizable compound 2 containing an amide bond is the same as the specific polymerizable compound 1 containing an amide bond, and the preferable mode and specific examples are the same.
[ Molecular weight ]
The molecular weight (weight average molecular weight when having a molecular weight distribution) of the specific polymerizable compound 2 is preferably 200 to 1,000, more preferably 200 to 800, and still more preferably 260 to 600.
[ Content ]
The content of the specific polymerizable compound 2 is preferably more than 0% by mass and 60% by mass or less relative to the total solid content of the composition in the second embodiment of the curable 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 specific polymerizable compound 2 may be used alone or in combination of 1 or more than 2. When 2 or more kinds are used simultaneously, the total amount thereof is preferably within the above range.
[ Valence of radical polymerizable group ]
The radical polymerizable group valence of the compound derived from the radical polymerizable group having a molecular weight of 2,000 or less, preferably 0.25mmol/g or more, more preferably 0.50mmol/g or more, relative to the total solid content of the composition when the composition contains the specific polymerizable compound 2.
< Onium salt >)
The curable resin composition of the present invention preferably contains an onium salt.
The kind of the onium salt is not particularly limited, and ammonium salts, imide salts, sulfonium salts, iodonium salts, or phosphonium salts are preferable.
Among them, ammonium salts or imide salts are preferable from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferable from the viewpoint of compatibility with the polymer.
The onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may be bonded via a covalent bond or may not be bonded via a covalent bond.
That is, the onium salt may be an intramolecular salt having a cation moiety and an anion moiety in the same molecular structure, or may be an intermolecular salt in which cation molecules and anion molecules of different molecules are ion-bonded, and is preferably an intermolecular salt. In the curable resin composition of the present invention, the cationic part or the cationic molecule and the anionic part or the anionic molecule may be bonded by ionic bonding or may be dissociated.
The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least 1 cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.
The onium salts used in the present invention may also be thermal alkaline generators.
The thermal alkaline generator is a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ℃ or higher.
[ Ammonium salt ]
In the present invention, ammonium salt means a salt of ammonium cation with anion.
Ammonium cations-
As the ammonium cation, a quaternary ammonium cation is preferable.
The ammonium cation is preferably a cation represented by the following formula (101).
[ Chemical formula 23]
In formula (101), R 1～R4 each independently represents a hydrogen atom or a hydrocarbon group, and at least 2 of R 1～R4 may be bonded to form a ring.
In the formula (101), R 1～R4 is each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and further preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R 1～R4 may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like.
When at least 2 of R 1～R4 are each bonded to form a ring, the ring may contain a heteroatom. The hetero atom may be a nitrogen atom.
The ammonium cation is preferably represented by any one of the following formulas (Y1-1) to (Y1-2).
[ Chemical formula 24]
In the formulae (Y1-1) and (Y1-2), R 101 represents an n-valent organic group, R 1 has the same meaning as R 1 in the formula (101), ar 101 and Ar 102 each independently represent an aryl group, and n represents an integer of 1 or more.
In the formula (Y1-1), R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon or a group in which n hydrogen atoms are removed from these bonded structures, more preferably a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms or a group in which n hydrogen atoms are removed from benzene or naphthalene.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.
In the formula (Y1-2), ar 101 and Ar 102 are each independently preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
Anions-
The anion in the ammonium salt is preferably selected from 1 of carboxylate anion, phenol anion, phosphate anion and sulfate anion, and more preferably carboxylate anion from the viewpoint of the stability of the salt and the thermal decomposition property. That is, the ammonium salt is more preferably a salt of an ammonium cation with a carboxylate anion.
The carboxylate anion is preferably an anion of a carboxylic acid having 2 or more valences of 2 or more carboxyl groups, more preferably an anion of a carboxylic acid having 2 or more valences. According to this aspect, the stability, curability, and developability of the curable resin composition can be further improved. In particular, by using an anion of a 2-valent carboxylic acid, the stability, curability, and developability of the curable resin composition can be further improved.
The carboxylate anion is preferably represented by the following formula (X1).
[ Chemical formula 25]
In the formula (X1), EWG represents an electron withdrawing group.
In the present embodiment, the electron withdrawing group means an electron withdrawing group in which the hamilt substituent constant σm represents a positive value. Among them, σm is described in detail in Dou Yexiong, pond, journal of Synthetic Organic Chemistry, japanese 23, vol.8 (1965) p.631-642. The electron withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents.
Examples of substituents in which σm represents a positive value include CF 3 group (σm=0.43), CF 3 C (=o) group (σm=0.63), hc≡c group (σm=0.21), CH 2 =ch group (σm=0.06), ac group (σm=0.38), meOC (=o) group (σm=0.37), meC (=o) ch=ch group (σm=0.21), phC (=o) group (σm=0.34), and H 2NC(＝O)CH2 group (σm=0.06). In addition, me represents methyl, ac represents acetyl, and Ph represents phenyl (hereinafter, the same applies).
EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).
[ Chemical formula 26]
In the formulae (EWG-1) to (EWG-6), R x1～Rx3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.
In the present invention, the carboxylate anion is preferably represented by the following formula (XA).
[ Chemical formula 27]
In the formula (XA), L 10 represents a single bond or a 2-valent bond selected from the group consisting of alkylene, alkenylene, aromatic group, -NR X -, and a combination of these, and R X represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.
Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetate anion and oxalate anion.
From the viewpoint that cyclization of a specific precursor is easy to be carried out at a low temperature and that storage stability of a curable resin composition is easy to be improved, the onium salt in the present invention preferably contains an ammonium cation as a cation and the onium salt contains an anion having a pKa (pKaH) of a conjugate acid of 2.5 or less as an anion, more preferably contains an anion of 1.8 or less.
The lower limit of the pKa is not particularly limited, but is preferably-3 or more, more preferably-2 or more, from the viewpoint that the produced base is not easily neutralized and the cyclization efficiency of a specific precursor or the like is improved.
As such pKa, reference can be made to the values described in Determination of Organic Structures by Physical Methods (authored: brown, H.C., mcDaniel, D.H., hafliger, O. Nachod, F.C.; authored: braude, E.A., nachod, F.C.; ACADEMIC PRESS, new York, 1955) or Data for Biochemical Research (authored: dawson, R.M.C.et al; oxford, clarendon Press, 1959). For the compounds not described in these documents, the values calculated by the structural formulae using software of ACD/pKa (manufactured by ACD/Labs) were used.
Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.
[ Chemical formula 28]
[ Imide salt ]
In the present invention, the imine salt means a salt of an imine cation with an anion. As the anion, the same anions as those in the ammonium salt described above can be exemplified, and the same preferable modes are also exemplified.
Imine cation-
As the imine cation, a pyridinium cation is preferable.
The imine cation is also preferably a cation represented by the following formula (102).
[ Chemical formula 29]
In formula (102), R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group, R 7 represents a hydrocarbon group, and at least 2 of R 5～R7 may be bonded to each other to form a ring.
In the formula (102), R 5 and R 6 have the same meaning as R 1～R4 in the above formula (101), and the preferable mode is also the same.
In formula (102), R 7 is preferably bonded to at least 1 of R 5 and R 6 to form a ring. The ring may contain heteroatoms. The hetero atom may be a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
The imine cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5).
[ Chemical formula 30]
In the formulae (Y1-3) to (Y1-5), R 101 represents an n-valent organic group, R 5 has the same meaning as R 5 in the formula (102), R 7 has the same meaning as R 7 in the formula (102), and n and m represent integers of 1 or more.
In the formula (Y1-3), R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon or a group in which n hydrogen atoms are removed from these bonded structures, more preferably a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms or a group in which n hydrogen atoms are removed from benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.
In the formula (Y1-5), m is preferably 1 to 4, more preferably 1 or 2, further preferably 1.
Specific examples of the imide salt include the following compounds, but the present invention is not limited thereto.
[ Chemical formula 31]
[ Sulfonium salt ]
In the present invention, sulfonium salt means a salt of sulfonium cation with anions. As the anion, the same anions as those in the ammonium salt described above can be exemplified, and the same preferable modes are also exemplified.
Sulfonium cations (S-S)
As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.
The sulfonium cation is preferably a cation represented by the following formula (103).
[ Chemical formula 32]
In formula (103), R 8～R10 each independently represents a hydrocarbon group.
R 8～R10 is preferably independently an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
R 8～R10 may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like. Among them, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R 8～R10 may be the same or different, and from the viewpoint of synthesis suitability, the same group is preferable.
Specific examples of the sulfonium salt include the following compounds, but the present invention is not limited thereto.
[ Chemical formula 33]
[ Iodized salt ]
In the present invention, the iodide salt means a salt of iodide cation with anion. As the anion, the same anions as those in the ammonium salt described above can be exemplified, and the same preferable modes are also exemplified.
Iodine cations-
As the iodide cation, a diaryliodonium cation is preferable.
Further, as the iodide cation, a cation represented by the following formula (104) is preferable.
[ Chemical formula 34]
In formula (104), R 11 and R 12 each independently represent a hydrocarbon group.
R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like. Among them, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R 11 and R 12 may be the same group or different groups, and from the viewpoint of synthesis suitability, the same group is preferable.
Specific examples of the iodide salt include the following compounds, but the present invention is not limited thereto.
[ Chemical formula 35]
[ Phosphonium salts ]
In the present invention, phosphonium salt means a salt of phosphonium cation and anion. As the anion, the same anions as those in the ammonium salt described above can be exemplified, and the same preferable modes are also exemplified.
Phosphonium cations-
The phosphonium cations are preferably quaternary phosphonium cations, and examples thereof include tetraalkylphosphonium cations, triarylmonoalkylphosphonium cations, and the like.
The phosphonium cation is preferably a cation represented by the following formula (105).
[ Chemical formula 36]
In formula (105), R 13～R16 each independently represents a hydrogen atom or a hydrocarbon group.
R 13～R16 is preferably independently an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
R 13～R16 may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like. Among them, the substituent is preferably an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and still more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
R 13～R16 may be the same or different, and from the viewpoint of synthesis suitability, the same group is preferable.
Specific examples of the phosphonium salts include the following compounds, but the present invention is not limited thereto.
[ Chemical formula 37]
When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass% or more, still more preferably 0.85 mass% or more, still more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, still more preferably 20 mass% or less, still more preferably 10 mass% or less, and may be 5 mass% or less, or may be 4 mass% or less.
The onium salt can be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably in the above range.
< Thermoalciferous agent >)
The curable resin composition of the present invention may contain a thermal alkaline generator.
The thermal alkaline generator may be a compound conforming to the onium salt, or may be a thermal alkaline generator other than the onium salt.
As the other thermal alkaline generator, nonionic thermal alkaline generators may be mentioned.
The nonionic thermal alkaline generator may be a compound represented by the formula (B1) or the formula (B2).
[ Chemical formula 38]
In the formula (B1) and the formula (B2), rb 1、Rb2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom, or a hydrogen atom. Wherein Rb 1 and Rb 2 do not simultaneously become hydrogen atoms. Moreover, neither Rb 1、Rb2 nor Rb 3 has a carboxyl group. In the present specification, the tertiary amine structure means a structure in which all of 3 bonds of a nitrogen atom having a valence of 3 are covalently bonded to a carbon atom of a hydrocarbon system. Therefore, when the bonded carbon atom is a carbonyl group-forming carbon atom, that is, when an amide group is formed together with a nitrogen atom, the present invention is not limited thereto.
In the formulae (B1) and (B2), at least 1 of Rb 1、Rb2 and Rb 3 preferably contains a cyclic structure, and more preferably at least 2 contain a cyclic structure. The cyclic structure may be any 1 of a single ring and a condensed ring, and preferably a single ring or a condensed ring in which 2 single rings are condensed. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, 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 and Rb 2 are preferably a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 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), or an aralkyl group (preferably 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms). These groups may have substituents within a range that exerts the effects of the present invention. Rb 1 and Rb 2 may be bonded to each other to form a ring. As the formed ring, a 4-to 7-membered nitrogen-containing heterocycle is preferable. In particular, rb 1 and Rb 2 are preferably 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), more preferably 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 still more preferably a cyclohexyl group which may have a substituent.
Examples of Rb 3 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, still more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an alkenyl group (preferably 2 to 24 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 carbon atoms). Among them, cycloalkyl groups are preferably (carbon number is preferably 3 to 24, more preferably 3 to 18, still more preferably 3 to 12), arylalkenyl groups, or arylalkoxy groups. Rb 3 may further have a substituent within the range where the effect of the present invention is exerted.
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
[ Chemical formula 39]
/>
Wherein Rb 11 and Rb 12 and Rb 31 and Rb 32 have the same meanings as Rb 1 and Rb 2 in formula (B1), respectively.
Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 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 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), and may have a substituent within a range that exerts the effect of the present invention. Among them, rb 13 is preferably an aralkyl group.
Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms), or a hydrogen atom.
Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 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 a preferable aryl group.
The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1 a).
[ Chemical formula 40]
Rb 11 and Rb 12 have the same meaning as Rb 11 and Rb 12 in formula (B1-1).
Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 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), a hydrogen atom or a methyl group.
Rb 17 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 12 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 an aryl group.
The molecular weight of the nonionic thermal alkaline 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.
Among the onium salts, the following compounds are exemplified as specific examples of the compounds as the thermal alkaline generator or specific examples of other thermal alkaline generators.
[ Chemical formula 41]
[ Chemical formula 42]
[ Chemical formula 43]
The content of the thermal alkaline generator is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass% or more, and still more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, and still more preferably 20 mass% or less. The thermal alkaline generator can be used in 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably in the above range.
< Photopolymerization initiator >)
The curable resin composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photo radical polymerization initiator. 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. And, may be an active agent that exerts some effect on the photosensitizing agent and generates active radicals.
The photo radical polymerization initiator preferably contains at least 1 compound having an absorbance of at least about 50 L.mol -1·cm-1 mol in the range of about 300 to 800nm (preferably 330 to 500 nm). The molar absorptivity of the compound can be measured by a known method. For example, it is preferable to conduct the measurement by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co.) and using an ethyl acetate solvent at a concentration of 0.01 g/L.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, 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 and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference is made to paragraphs 0138 to 0151 of Japanese patent application laid-open No. 2016-027357 and International publication No. 2015/199219, 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. Of the commercial products, KAYACURE DETX (manufactured by Nippon Kayaku co., ltd.) is also preferably used.
As the photo radical polymerization initiator, it is also possible to preferably use hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds. More specifically, for example, an aminoacetophenone initiator described in Japanese patent application laid-open No. 10-291969 or an acylphosphine oxide initiator described in Japanese patent application laid-open No. 4225898 can be used.
As the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade names: all are manufactured by BASF corporation) can be used.
As the aminoacetophenone initiator, IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade name: all manufactured by BASF corporation) which are commercially available products can be used.
As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179 having an absorption maximum wavelength matching a light source having a wavelength of 365nm or 405nm or the like can be used.
Examples of the acylphosphine initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Further, IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF corporation) can be used as a commercial product.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF corporation).
As the photo radical polymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be further effectively improved. Among oxime compounds, those having a wide exposure latitude (exposure margin) and also functioning as a photocuring accelerator are particularly preferable.
Specific examples of the oxime compound include a compound described in JP-A-2001-233836, a compound described in JP-A-2000-080068, and a compound described in JP-A-2006-342166.
Preferable oxime compounds include, for example, 3-benzoyloxy iminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxy iminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino1-phenylpropane-1-one, 2-benzoyloxy imino1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy imino1-phenylpropane-1-one having the following structures. In the curable resin composition of the present invention, an oxime compound (oxime-based photopolymerization initiator) is particularly preferably used as a photo radical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > c=n-O-C (=o) -in the molecule.
[ Chemical formula 44]
Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above is manufactured by BASF corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, japanese patent application laid-open No. 2012-014052) may also be preferably used. Also, TR-PBG-304 (Changzhou Tronly New Electronic Materials CO., LTD.; manufactured by LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Further, DFI-091 (DAITO CHEMIX Co., ltd.) can be used.
Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include a compound described in JP 2010-26261028A, a compound 24, 36 to 40 described in paragraph 0345 of JP 2014-500852A, and a compound (C-3) described in paragraph 0101 of JP 2013-164471A.
The most preferable oxime compound includes 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.
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 a trihalomethyl oxazine compound, an α -amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, further preferred is at least 1 compound selected from the group consisting of a trihalomethyl triazine compound, an α -amino ketone compound, an oxime compound, a triarylimidazole dimer, a benzophenone compound, still further preferred is a metallocene compound or an oxime compound, and still further preferred is an oxime compound.
The photo radical polymerization initiator may be a benzoin compound such as benzophenone, N ' -tetramethyl-4, 4' -diaminobenzophenone (Michler's ketone), a benzoin compound such as benzoin, alkyl benzoin, or a benzyl derivative such as benzyl dimethyl ketal, and an aromatic ketone such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinophenone-1, or an alkylanthraquinone fused with an aromatic ring. Further, a compound represented by the following formula (I) can also be used.
[ Chemical formula 45]
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, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a phenyl group or a biphenyl group substituted by at least 1 of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms interrupted by 1 or more oxygen atoms, R I01 is a group represented by the formula (II) or the same group as R I00, and R I02～RI04 is each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a halogen atom.
[ Chemical formula 46]
Wherein R I05～RI07 is the same as R I02～RI04 of formula (I) above.
The photo radical polymerization initiator may be any of the compounds described in paragraphs 0048 to 0055 of International publication No. 2015/125469.
When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, 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 curable 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 above ranges are preferable in total.
< Thermal polymerization initiator >)
As the polymerization initiator, the curable 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 the energy of heat and initiates or accelerates the polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, cyclization of the heterocyclic polymer-containing precursor can be performed and polymerization of the heterocyclic polymer-containing precursor can be performed, so that higher heat resistance can be achieved.
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.
When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass, relative to the total solid content of the curable resin composition of the present invention. The thermal radical polymerization initiator may be contained in an amount of 1 or 2 or more. When the thermal radical polymerization initiator is contained in an amount of 2 or more, the above-mentioned ranges are preferable in total.
< Other polymerizable Compound >
[ Other radically polymerizable Compounds ]
The curable resin composition of the present invention preferably contains a different polymerizable compound from the specific polymerizable compound.
The compound contained in the specific polymerizable compound is not contained in other polymerizable compounds.
As the other polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. Examples of the radical polymerizable group include a group containing an ethylenic unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group. The radical polymerizable group is preferably a (meth) acryloyl group, and from the viewpoint of reactivity, a (meth) acryloyloxy group is more preferable.
The number of radical polymerizable groups in the radical polymerizable compound may be 1 or 2 or more, and the radical polymerizable compound preferably has 2 or more radical polymerizable groups, more preferably 3 or more. The upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.
The molecular weight of the radical polymerizable compound 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 polymerizable compound is preferably 100 or more.
From the viewpoint of developability, the curable resin composition of the present invention preferably contains at least 1 radical polymerizable compound having 2 or more functions containing 2 or more radical polymerizable groups, more preferably contains at least 1 radical polymerizable compound having 3 or more functions. And, it may be a mixture of a 2-functional radical polymerizable compound and a 3-functional or more radical polymerizable compound. For example, the number of functional groups of the polymerizable monomer having 2 or more functions means that the number of radical polymerizable groups in 1 molecule is 2 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 esters of unsaturated carboxylic acids and polyhydric alcohol compounds are preferable. In addition, an addition reaction product of an unsaturated carboxylic acid ester having an affinity substituent such as a hydroxyl group, an amino group, a mercapto group, or the like with a monofunctional epoxy compound, a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, or the like can be preferably used. Also, addition reactants of unsaturated carboxylic acid esters having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, and substitution reactants of unsaturated carboxylic acid esters having releasable substituents such as halogen groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines and thiols are preferable. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like can be used. 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 polymerizable compound preferably has a boiling point of 100℃or higher at normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tri (acryloxyethyl) isocyanato, glycerol or trimethylolethane, and the like, and polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acids, which are obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols, and (meth) acrylation, as described in Japanese patent application laid-open No. 48-064183, japanese patent application laid-open No. 49-043191, and Japanese patent application laid-open No. 52-030490; and mixtures of these. Further, 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 ethylenic unsaturated bond such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid can also be mentioned.
Further, as a preferable radical polymerizable compound other than the above, a compound having a fluorene ring and having 2 or more groups containing ethylenic unsaturated bonds or a cardo (cardo) resin described in japanese unexamined patent publication No. 2010-160418, japanese unexamined patent publication No. 2010-129825, japanese patent publication No. 4364216, and the like can be used.
Further, examples of the compounds include specific unsaturated compounds described in Japanese patent publication No. 46-043946, japanese patent publication No. 01-040337, 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, pages 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 as the formula (1) and the formula (2) in JP-A-10-062986, and specific examples thereof, can also be used as radical polymerizable compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resultant.
The compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as other radical polymerizable compounds, and these are incorporated herein.
The radical polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330;Nippon Kayaku Co, manufactured by Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320;Nippon Kayaku Co, manufactured by Ltd., A-TMMT: shin-Nakamura Chemical Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310;Nippon Kayaku Co, manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; nippon Kayaku Co., manufactured by Ltd., A-DPH; shin-Nakamura Chemical Co., manufactured by Ltd.), or a structure in which these (meth) acryl groups are bonded via a glycol residue or a propylene glycol residue. These oligomer types can also be used.
Examples of the commercially available products of the radical polymerizable compound include SR-494, which is a 4-functional acrylate having 4 ethyleneoxy chains, made by Sartomer Company, inc, sartomer Company, which is a 2-functional methyl acrylate having 4 ethyleneoxy chains, SR-209, 231, 239, nippon Kayaku Co., ltd., DPCA-60, which is a 6-functional acrylate having 6 ethyleneoxy chains, made by Ltd., TPA-330, which is a 3-functional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 (NIPPON PAPER INDUSTRIES CO., LTD., ltd.), NK ester M-40G, NK ester M-9300, NK ester A-9300, UA-7200 (Shin-Nakamura Chemical Co., ltd.), DPHA-40H (Nippon Kayaku Co., ltd.), UA-306, UA-29, and UF-600, made by PME.600, and so on.
Further, as the radical polymerizable compound, a compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.
The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphate group. Among the radically polymerizable compounds having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a radically polymerizable compound having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride is more preferable. Particularly, among the radically polymerizable compounds having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, a compound of pentaerythritol or dipentaerythritol is preferable. Examples of the commercially available products include polyacid-modified acrylic oligomers produced by TOAGOSEI CO., ltd. Include M-510 and M-520.
The acid value of the radical polymerizable compound having an acid group is preferably 0.1 to 40mgKOH/g, particularly preferably 5 to 30mgKOH/g. The radical polymerizable compound has an acid value within the above range, and therefore, the composition is excellent in handling properties in production and further excellent in developability. And, the polymerizability is good. The acid value was in accordance with JIS K0070: 1992.
The curable resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film. As the monofunctional radical polymerizable compound, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate and other allyl compounds can be preferably used. The monofunctional radical polymerizable compound is preferably a compound having a boiling point of 100 ℃ or higher at normal pressure in order to suppress volatilization before exposure.
[ Polymerizable Compound other than the radically polymerizable Compound described above ]
The curable resin composition of the present invention may further contain a polymerizable compound other than the radical polymerizable compound as the other polymerizable compound. Examples of the polymerizable compound other than the radical polymerizable compound include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; oxetane compounds; a benzoxazine compound.
Compounds having hydroxymethyl, alkoxymethyl or acyloxymethyl groups
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM 1), (AM 4) or (AM 5) is preferable.
[ Chemical formula 47]
(Wherein t represents an integer of 1 to 20, R 104 represents a t-valent organic group having 1 to 200 carbon atoms, R 105 represents a group represented by-OR 106 OR-OCO-R 107, R 106 represents a hydrogen atom OR an organic group having 1 to 10 carbon atoms, and R 107 represents an organic group having 1 to 10 carbon atoms.)
[ Chemical formula 48]
(Wherein R 404 represents a 2-valent organic group having 1 to 200 carbon atoms, R 405 represents a group represented by-OR 406 OR-OCO-R 407, R 406 represents a hydrogen atom OR an organic group having 1 to 10 carbon atoms, and R 407 represents an organic group having 1 to 10 carbon atoms.)
[ Chemical formula 49]
(Wherein u represents an integer of 3 to 8, R 504 represents a u-valent organic group having 1 to 200 carbon atoms, R 505 represents a group represented by-OR 506 OR-OCO-R 507, R 506 represents a hydrogen atom OR an organic group having 1 to 10 carbon atoms, and R 507 represents an organic group having 1 to 10 carbon atoms.)
Specific examples of the compound represented by the formula (AM 4) include 46DMOC, 46DMOEP (trade name above, trade name above )、DML-MBPC、DML-MBOC、DML-OCHP、DML-PCHP、DML-PC、DML-PTBP、DML-34X、DML-EP、DML-POP、dimethylolBisOC-P、DML-PFP、DML-PSBP、DML-MTrisPC( manufactured by ASAHI YUKIZAI CORPORATION, trade name above Honshu Chemical Industry co., manufactured by ltd.) and NIKALAC MX-290 (trade name, SANWA CHEMICAL co., manufactured by ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2, 6-dimethoxymethyl-4-tert-butylphenol), 2,6-dimethoxymethyl-p-cresol (2, 6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2, 6-diacetoxymethyl-p-cresol), and the like.
Specific examples of the compound represented by the formula (AM 5) include TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPA、TMOM-BP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP( or more under the trade name Honshu Chemical Industry co, manufactured by ltd.), TM-BIP-a (under the trade name ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (under the trade name SANWA CHEMICAL co., manufactured by ltd.).
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 is less likely to cause film shrinkage because it does not cause a dehydration reaction derived from crosslinking. Therefore, by containing the epoxy compound, low-temperature curing and warpage of the curable resin composition 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 means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
Examples of the epoxy compound include bisphenol a type epoxy resins; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-containing silicones such as polymethyl (glycidoxypropyl) siloxane, etc., but are not limited thereto. Specifically, examples thereof include EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (manufactured by DIC Corporation), RIKARESIN (registered trademark) O-60E (manufactured by BE92 Co., ltd.), EP-4003S, EP-4000S (manufactured by ADEKA CORPORATION). Among them, an epoxy resin containing a polyethylene oxide group is preferable in view of suppression of warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, RIKARESIN (registered trademark) BEO-60E contains a polyethylene oxide group, and is preferable.
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-hydroxymethyloxetane, 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. As a specific example, TOAGOSEI CO. LTD ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these may be used alone or 2 or more may be mixed.
Benzoxazine compound (compound having polybenzoxazole group)
The benzoxazine compound is preferable because it does not generate outgas during curing due to a crosslinking reaction resulting from a ring-opening addition reaction, and further reduces heat shrinkage to suppress warpage.
Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (trade name, shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and novolak type dihydrobenzoxazine compounds. These may be used alone, or 2 or more kinds may be mixed.
When the other polymerizable compound 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 curable 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 other polymerizable compounds may be used alone or in combination of 1 or more than 2. When 2 or more kinds are used simultaneously, the total amount thereof is preferably within the above range.
< Solvent >
The curable 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 compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of the esters include preferable esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, 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-ethoxypropionate, etc. (e.g., methyl 2-ethoxypropionate, etc.), ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like.
Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
Examples of the aromatic hydrocarbon include toluene, xylene, anisole, and limonene.
Examples of the sulfoxides include dimethyl sulfoxide, which is a preferred sulfoxide.
As the amides, preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, and the like.
The solvent is preferably mixed with 2 or more types from the viewpoint of improvement of the properties of the coated surface, etc.
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, and propylene glycol methyl ether acetate. It is particularly preferable to use dimethyl sulfoxide and gamma-butyrolactone simultaneously.
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 40 to 70% by mass of the total solid content concentration of the curable resin composition of the present invention from the viewpoint of coatability. The content of the solvent may be adjusted according to the desired thickness and coating method.
The solvent may contain only 1 or 2 or more kinds. When the solvent is contained in an amount of 2 or more, the above-mentioned ranges are preferable in total.
Migration inhibitor
The curable 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 curable resin composition layer can be effectively inhibited.
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), compounds having thiourea and a mercapto group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
Alternatively, an ion scavenger that traps anions such as halogen 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.
Specific examples of migration inhibitors include the following compounds.
[ Chemical formula 50]
When the curable resin composition 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% based on the total solid content of the curable resin composition.
The migration inhibitor may be 1 or 2 or more. When the migration inhibitor is 2 or more, the above ranges are preferable in total.
< Polymerization inhibitor >)
The curable resin composition of the present invention preferably contains a polymerization inhibitor.
As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, 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-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-t-butyl) phenylmethane and the like can be preferably used. Further, a polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International publication No. 2015/125469 can also be used.
In addition, the following compound (Me is methyl) can also be used.
[ Chemical formula 51]
When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.05 to 2.5% by mass, relative to the total solid content of the curable 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 above range is preferable in total.
Metal adhesion improver
The curable 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. As the metal adhesion improver, a silane coupling agent and the like can be mentioned.
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 publication No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-04264, and a compound described in paragraph 0055 of International publication No. 2014/097594. It is also preferable to use 2 or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. The silane coupling agent is preferably the following compound. In the following formula, et represents ethyl.
[ Chemical formula 52]
Further, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP-A2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A2013-072935 can be used.
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 0.5 to 15 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 heterocyclic polymer-containing precursor. By setting the lower limit value or more, the adhesion between the cured film after the curing step and the metal layer is improved, and by setting the upper limit value or less, the heat resistance and mechanical properties of the cured film after the curing step are improved. The metal adhesion improver may be 1 or 2 or more. When 2 or more kinds are used, the above ranges are preferable in total.
< Other additives >)
The curable resin composition of the present invention may contain various additives, for example, a sensitizer such as a thermal acid generator or N-phenyldiethanolamine, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, a coagulation inhibitor, and the like, as required, within a range that does not impair the effects of the present invention. When these additives are blended, the total blending amount is preferably 3 mass% or less of the solid content of the curable resin composition.
[ Sensitizer ]
The curable resin composition of the present invention 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 heat curing accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and causes the effects of electron transfer, energy transfer, heat generation, or the like. Thus, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed to decompose and generate radicals, acids, or bases.
Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine.
As the sensitizer, a sensitizing dye may 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 is incorporated herein by reference.
When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total solid content of the curable resin composition of the present invention. The sensitizer may be used alone or in combination of 1 or more than 2.
[ Chain transfer agent ]
The curable 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 (The Society of Polymer Science, japan, 2005). As the chain transfer agent, for example, a compound group having SH, PH, siH and GeH in the molecule is used. These supply hydrogen to the low-activity radicals to generate radicals, or after oxidation, the radicals can be generated by deprotonation. 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.
When the curable 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 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the curable 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 above ranges are preferable in total.
[ Surfactant ]
From the viewpoint of further improving coatability, various surfactants may be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The following surfactants are also preferred. In the following formula, brackets indicating structural units of the main chain indicate the content (mol%) of each structural unit, and brackets indicating structural units of the side chain indicate the number of repetitions of each structural unit.
[ Chemical formula 53]
The surfactant may be a compound described in paragraphs 0159 to 0165 of International publication No. 2015/199219.
When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the curable resin composition of the present invention. The number of surfactants may be 1 or 2 or more. When the surfactant is 2 or more, the above-mentioned ranges are preferable in total.
[ 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 curable resin composition of the present invention so as to be biased to the surface of the curable resin composition during drying after coating.
Further, a compound described in paragraph 0155 of International publication No. 2015/199219 can also be used as the higher fatty acid derivative.
When the curable 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 curable 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 above ranges are preferable in total.
< Restriction on other substances contained >
From the viewpoint of the coating surface properties, the moisture content of the curable resin composition of the present invention is preferably less than 5 mass%, more preferably less than 1 mass%, and even more preferably less than 0.6 mass%.
From the viewpoint of insulation properties, the metal content of the curable 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, chromium, and nickel. When a plurality of metals are contained, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities accidentally contained in the curable resin composition of the present invention, the following method can be mentioned: a method in which a raw material having a small metal content is selected as a raw material constituting the curable resin composition of the present invention, the raw material constituting the curable resin composition of the present invention is filtered through 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 view of the use as a semiconductor material and from the viewpoint of wiring corrosiveness, the content of halogen atoms in the curable resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, the halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably in the above range.
As the container for the curable resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, a multilayer bottle having 6 types of 6 layers of resins constituting the inner wall of the container and a bottle having 6 types of resins in a 7-layer structure are preferably used in order to prevent impurities from being mixed into the raw material or the curable resin composition. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351.
Preparation of curable resin composition
The curable 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.
In order to remove foreign matters such as dust and particles in the curable resin composition, filtration using a filter is preferably performed. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be a filter previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be used in parallel or in series. When a plurality of filters are used, filters having different pore diameters or materials may be used in combination. And, various materials may be filtered multiple times. When the filtration is performed a plurality of times, the filtration may be a cyclic filtration. And, filtration may be performed after pressurization. When filtration is performed after pressurization, the pressure at which pressurization is performed is preferably 0.05MPa or more and 0.3MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. 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.
Use of curable resin composition
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
Further, the method can be used for forming an insulating film, a stress buffer film, and the like of a semiconductor device.
(Cured film, laminate, semiconductor device, and method for producing the same)
Next, a cured film, a laminate, a semiconductor device, and methods for manufacturing these will be described.
The cured film of the present invention is obtained by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more and 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less.
The cured film of the present invention may be laminated in 2 or more layers, and further in 3 to 7 layers, to form a laminate. The laminate of the present invention preferably contains 2 or more cured films, and any of the cured films contains a metal layer between them. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.
Examples of the field to which the cured film 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 an insulating film for the above-mentioned practical mounting use is etched to form a pattern, 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", 4 th month in 2008, yo-yo/prison, foundation and development of polyimide materials by CMC Technology library ", release 11 th month in 2011, and japanese polyimide/aromatic polymer research institute/code" latest polyimide foundation and application ", NTS, 8 th month in 2010, and the like.
The cured film of the present invention can be used for the production of a plate surface such as an offset plate surface or a screen plate surface, the use of an etching-molded member, the production of a protective varnish and a dielectric layer in electronics, particularly microelectronics, and the like.
The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") preferably includes a film forming step of forming a film by applying the curable resin composition of the present invention to a substrate.
The method for producing a cured film according to the present invention preferably includes the film formation step, an exposure step of exposing the film, and a development step of developing the film.
The method for producing a cured film according to the present invention further preferably includes the film formation step and the development step as needed, and further includes a heating step of heating the film at 50 to 450 ℃.
Specifically, the method preferably includes the following steps (a) to (d).
(A) Film formation step of forming film (curable resin composition layer) by applying curable resin composition to substrate
(B) An exposure step of exposing the film after the film formation step
(C) A developing step of developing the exposed film
(D) A heating step of heating the developed film at 50-450 DEG C
By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the thermal alkaline generator is decomposed, and sufficient curability can be obtained.
The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film according to the present invention. The method for producing a laminate according to the present embodiment further includes the steps (a) to (c) or (a) to (d) after forming the cured film according to the method for producing a cured film described above. In particular, the above steps are sequentially performed a plurality of times, for example, preferably 2 to 5 times (i.e., 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on or between the cured films of the portion where the cured film is provided, or both. In addition, in the production of the laminate, it is not necessary to repeat all of the steps (a) to (d), and as described above, the laminate of the cured film can be obtained by performing at least the steps (a), preferably (a) to (c) or (a) to (d) a plurality of times.
Film formation step (layer formation step) >, and method for producing a film
The production method according to a preferred embodiment of the present invention includes a film formation step (layer formation step) of forming a film (layer) by applying the curable resin composition to a substrate.
The type of the substrate can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc., metal substrates such as quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, ni, cu, cr, fe, etc., papers, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of Plasma Display Panels (PDP), etc. In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate is more preferable.
As the base material, for example, a plate-shaped base material (substrate) is used.
When the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.
As a method for applying the curable resin composition to a substrate, coating is preferable.
Specifically, 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. From the viewpoint of uniformity of thickness of the curable resin composition layer, spin coating, slit coating, spray coating, and inkjet method are more preferable. By adjusting the appropriate solid content concentration and coating conditions according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and spin coating, spray coating, ink jet method, or the like is preferable as long as the substrate is a circular substrate such as a wafer, and slit coating, spray coating, ink jet method, or the like is preferable as long as the substrate is a rectangular substrate. In the case of spin coating, for example, a spin speed of 500 to 2,000rpm can be applied for about 10 seconds to 1 minute.
The present invention is also applicable to a method of transferring a coating film formed by the above-described application method to a pseudo support in advance onto a substrate.
In the present invention, the transfer method can be preferably used as the production method described in paragraphs 0023, 0036 to 0051 of Japanese patent application laid-open No. 2006-023696 or 0096 to 0108 of Japanese patent application laid-open No. 2006-047592.
< Drying Process >)
The production method of the present invention may further include a step of drying the film (curable resin composition layer) after the film forming step (layer forming step) to remove the solvent. The drying temperature is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, still more preferably 90 to 110 ℃. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
< Exposure procedure >
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer) to light. The exposure amount is not particularly limited as long as the curable resin composition can be cured, and for example, it is preferably 100 to 10,000mJ/cm 2, more preferably 200 to 8,000mJ/cm 2, in terms of exposure energy at 365 nm.
The exposure wavelength can be appropriately set in the range of 190 to 1,000nm, preferably 240 to 550nm.
The exposure wavelength is described in relation to a light source, and examples thereof include (1) a semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm 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), wide (3 wavelengths of g, h, i-rays), (4) an excimer laser, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F 2 excimer laser (wavelength 157 nm), and an extreme ultraviolet (5); EUV (wavelength 13.6 nm), (6) electron beam, etc. The curable resin composition of the present invention is particularly preferably exposed by a high-pressure mercury lamp, and among these, exposure by i-rays is preferable. Thus, particularly high exposure sensitivity can be obtained.
< Procedure of developing treatment >
The production method of the present invention may include a development treatment step of developing the exposed film (curable resin composition layer) (developing the film). By performing development, an unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as a desired pattern can be formed, and for example, spin-coating immersion, spraying, dipping, ultrasonic wave, or other development methods can be employed.
The development is performed using a developer. The developer is not particularly limited as long as the unexposed portion (non-exposed portion) can be removed. The developer preferably contains an organic solvent, and the developer more preferably contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, more preferably contains an organic solvent having a ClogP value of 0 to 3. ClogP values can be obtained as calculated values by inputting structural formulae into chembio draw (chembio map).
As the organic solvent, for example, ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, ethyl 2-alkoxypropionate), 2-alkoxymethyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxymethyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate, etc., methyl 2-ethoxymethyl 2-ethoxypropionate, etc. preferable examples are mentioned 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 acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, and the like, and as sulfoxides, dimethyl sulfoxide, and the like, may be preferably, for example, be cited.
In the present invention, cyclopentanone, preferably gamma-butyrolactone, more preferably cyclopentanone, is used.
The developer is preferably an organic solvent in an amount of 50 mass% or more, more preferably an organic solvent in an amount of 70 mass% or more, and still more preferably an organic solvent in an amount of 90 mass% or more. Further, 100 mass% of the developer may be an organic solvent.
The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, and can be usually set at 20 to 40 ℃.
After the treatment with the developer, further rinsing may be performed. The rinsing is preferably performed with a solvent different from the developer. For example, the curable resin composition may be rinsed with a solvent. The rinsing time is preferably 5 seconds to 1 minute.
< Heating Process >)
The production method of the present invention preferably includes a heating step (heating step) of heating the developed film at 50 to 450 ℃.
The film forming step (layer forming step), the drying step, and the developing step are preferably followed by a heating step. In the heating step, for example, the thermal alkaline generator is decomposed to generate an alkali, and the cyclization reaction of the heterocyclic polymer precursor is performed. Further, curing of a specific polymerizable compound and other polymerizable compounds added as needed can be performed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 140 ℃ or higher, still more preferably 150 ℃ or higher, still more preferably 160 ℃ or higher, and still more preferably 170 ℃ or higher. The upper limit is preferably 500℃or less, more preferably 450℃or less, still more preferably 350℃or less, still more preferably 250℃or less, and still more preferably 220℃or less.
The heating is preferably performed at a heating rate of 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and still more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the highest heating temperature. The heating rate is set to 1 ℃/min or more, whereby the excessive volatilization of amine can be prevented while ensuring productivity, and the residual stress of the cured film can be relaxed by setting the heating rate to 12 ℃/min or less.
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 is the temperature at the start of the step of heating to the highest heating temperature. For example, when the curable resin composition is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably gradually increased from a temperature lower than the boiling point of the solvent contained in the curable resin composition by 30 to 200 ℃.
The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and still more preferably 30 to 240 minutes.
In particular, when forming a multilayer laminate, the heating temperature is preferably 180 to 320 ℃, more preferably 180 to 260 ℃, from the viewpoint of adhesion between layers of the cured film. The reason for this is not necessarily clear, but it is considered that the acetylene groups of the heterocyclic polymer precursors between the layers undergo a crosslinking reaction by setting the temperature to this value.
The heating may be performed in stages. As an example, a pretreatment process of raising the temperature from 25 ℃ to 180 ℃ at 3 ℃/min and holding at 180 ℃ for 60 minutes, raising the temperature from 180 ℃ to 200 ℃ at2 ℃/min and holding at 200 ℃ for 120 minutes may be performed. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform the treatment while irradiating ultraviolet rays, as described in U.S. Pat. No. 9159547. The film characteristics can be improved by these pretreatment steps. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be a two-stage or more process, and for example, the pretreatment process 1 may be performed at 100 to 150 ℃ and the pretreatment process 2 may be performed at 150 to 200 ℃.
The cooling may be performed after the heating, and the cooling rate in this case is preferably 1 to 5 ℃.
In the heating step, it is preferable to perform the heating step in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, for example, in order to prevent decomposition of the heterocyclic polymer precursor. The oxygen concentration is preferably 50ppm (volume ratio) or less, more preferably 20ppm (volume ratio) or less.
< Metal layer Forming Process >)
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after the development treatment.
The metal layer is not particularly limited, and a conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper.
The method for forming the metal layer is not particularly limited, and 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, and Japanese patent application laid-open No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating may be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, in the thickest wall thickness portion.
< Lamination Process >)
The production method of the present invention preferably further includes a lamination step.
The lamination step is a series of steps including (a) a film formation step (layer formation step), (b) an exposure step, (c) a development treatment step, and (d) a heating step, again performed in this order on the surface of the cured film (resin layer) or the metal layer. Here, the film formation step (a) may be repeated only. The heating step (d) may be performed at the end or in the middle of lamination. That is, the following modes may be adopted: repeating the steps (a) to (c) a predetermined number of times, and thereafter heating the laminated curable resin composition layers to cure the laminated curable resin composition layers. The developing step (c) may be followed by a metal layer forming step (e), and the heating of (d) may be performed each time or may be performed all at once after being laminated a predetermined number of times. It is needless to say that the lamination step may include the above-described drying step, heating step, and 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 heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, a plasma treatment is exemplified.
The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, the resin layer such as a resin layer/metal layer/resin layer/metal layer is preferably 3 or more and 7 or less, more preferably 3 or more and 5 or less.
In the present invention, in particular, after the metal layer is provided, it is preferable that a cured film (resin layer) of the curable resin composition is further formed so as to cover the metal layer. Specifically, there may be mentioned a method in which (a) the film forming step, (b) the exposing step, (c) the developing step, (e) the metal layer forming step, and (d) the heating step are sequentially repeated, or a method in which (a) the film forming step, (b) the exposing step, (c) the developing step, and (e) the metal layer forming step are sequentially repeated, and (d) the heating step is provided at the end or in the middle. By alternately performing the lamination step of laminating the curable resin composition layers (resin layers) and the metal layer formation step, the curable resin composition layers (resin layers) and the metal layers can be alternately laminated.
The invention also discloses a semiconductor device comprising the cured film or laminate of the invention. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used for formation of 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 jp 2016-027357 a, and these are incorporated herein by reference.
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, processing contents, processing steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. 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 example 1 >
[ Synthesis of polyimide precursor derived from pyromellitic dianhydride, 4' -diaminodiphenyl ether and benzyl alcohol (A-1: polyimide precursor having no radical polymerizable group) ]
14.06G (64.5 mmol) of pyromellitic dianhydride (dried at 140℃for 12 hours) and 14.22g (131.58 mmol) of benzyl alcohol were suspended in 50mL of N-methylpyrrolidone and dried over molecular sieves. The suspension was heated at 100℃for 3 hours. The reaction mixture was cooled to room temperature and 21.43g (270.9 mmol) of pyridine and 90mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to-10℃and 16.12g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at-10.+ -. 4 ℃. During the addition of SOCl 2, the viscosity increased. After dilution with 50mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution in which 11.08g (58.7 mmol) of 4,4' -diaminodiphenyl ether was dissolved in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-5 to 0℃over 20 minutes. Then, after the reaction mixture was reacted at 0℃for 1 hour, 70g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5,000rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred in 4 liters of water for 30 minutes again, and filtration was performed again. Next, the obtained polyimide precursor was dried at 45 ℃ for 3 days under reduced pressure. The polyimide precursor had a weight average molecular weight of 18,000.
[ Chemical formula 54]
Synthesis example 2
[ Synthesis of polyimide precursor derived from pyromellitic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-2: polyimide precursor having radical polymerizable group) ]
14.06G (64.5 mmol) of pyromellitic 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 diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60℃for 18 hours, whereby a diester of pyromellitic acid and 2-hydroxyethyl methacrylate was produced. Next, after the obtained diester was chlorinated by SOCl 2, the polyimide precursor was converted with 4,4' -diaminodiphenyl ether in the same manner as in synthesis example 1, and the polyimide precursor was obtained in the same manner as in synthesis example 1. The polyimide precursor had a weight average molecular weight of 19,000.
[ Chemical formula 55]
Synthesis example 3 >
[ Synthesis of polyimide precursor derived from 4,4 '-oxydiphthalic anhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: polyimide precursor having radical polymerizable group) ]
20.0G (64.5 mmol) of 4,4 '-oxydiphthalic 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 diglyme were mixed and stirred at 60℃for 18 hours to produce a diester of 4,4' -oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Next, after the obtained diester was chlorinated by SOCl 2, the polyimide precursor was converted with 4,4' -diaminodiphenyl ether in the same manner as in synthesis example 1, and the polyimide precursor was obtained in the same manner as in synthesis example 1. The polyimide precursor had a weight average molecular weight of 18,000.
[ Chemical formula 56]
Synthesis example 4 >
[ Synthesis of polyimide precursor (A-4: polyimide precursor having radical polymerizable group) derived from 4,4' -oxydiphthalic anhydride, 4' -diamino-2, 2' -dimethylbiphenyl (o-tolidine) and 2-hydroxyethyl methacrylate ]
20.0G (64.5 mmol) of 4,4 '-oxydiphthalic 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 diglyme were mixed and stirred at 60℃for 18 hours to produce a diester of 4,4' -oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Next, after the obtained diester was chlorinated by SOCl 2, the polyimide precursor was converted with 4,4 '-diamino-2, 2' -dimethylbiphenyl in the same manner as in synthesis example 1, and the polyimide precursor was obtained in the same manner as in synthesis example 1. The polyimide precursor had a weight average molecular weight of 19,000.
[ Chemical formula 57]
/>
Synthesis example 5 >
[ Synthesis of polyimide precursor derived from 4,4 '-oxydiphthalic anhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-5: polyimide precursor having radical polymerizable group) ]
155.1G of 4,4' -oxydiphthalic anhydride (ODPA) was placed in a 2 liter-capacity separation 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 a further 16 hours.
Then, under ice-cooling, 206.3g of Dicyclohexylcarbodiimide (DCC) was added to the reaction mixture with stirring for 40 minutes in 180ml of gamma-butyrolactone. Subsequently, a suspension of 93.0g of 4,4' -diaminodiphenyl ether in 350ml of gamma-butyrolactone was added over 60 minutes with stirring. After stirring for 2 hours at room temperature, 30ml of ethanol was added and stirred for 1 hour. Thereafter, 400ml of gamma-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, whereby 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-5 was obtained in the form of a powder. As a result of measurement of the weight average molecular weight (Mw) of this polymer A-5, it was 20,000.
Synthesis example 6 >
[ Synthesis of polyimide precursor (A-7: polyimide precursor having radical polymerizable group) derived from 3,3'4,4' -biphenyltetracarboxylic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate ]
In Synthesis example 5, a reaction was carried out in the same manner as described in Synthesis example 5 except that 147.1g of 3,3'4,4' -biphenyltetracarboxylic dianhydride was used in place of 155.1g of 4,4' -oxydiphthalic anhydride, thereby obtaining polymer A-6. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 22,000.
Synthesis example 7 >
[ Synthesis of Compound C-1 ]
Light acrylic ester PE-3A (KYOEISHA CHEMICAL Co., LTD.) was added dropwise to a mixture of hexamethylene diisocyanate and dibutyltin dilaurate or other catalyst heated to 30 to 90℃and allowed to react for 6 to 12 hours, thereby synthesizing compound C-1.
Synthesis example 8
[ Synthesis of Compound C-2 ]
In the synthesis of the compound C-1, the compound C-2 was synthesized in the same manner as in the synthesis of the compound C-1 except that hexamethylene diisocyanate was changed to isophorone diisocyanate.
Synthesis example 9 >
[ Synthesis of Compound C-3 ]
Under ice-cooling, p-xylylenediamine (manufactured by Karenz BEI (SHOWA DENKO K.) was added dropwise thereto and allowed to react at room temperature for 6 to 12 hours, thereby synthesizing compound C-3.
< Synthesis example 10 >
[ Synthesis of Compound C-4 ]
Compound C-4 was synthesized by reference to the synthesis method described in JP 2012-206992A.
Synthesis example 11
[ Synthesis of Compound C-5 ]
1,2, 4-Butanetriol is added dropwise to a mixture of Karenz MOI and dibutyltin dilaurate or other catalyst heated to 30 to 90 ℃ and allowed to react for 6 to 12 hours, thereby synthesizing compound C-5.
Synthesis example 12
[ Synthesis of Compound C-6 ]
2-Aminoethyl methacrylate hydrochloride was added dropwise to 1,3, 5-benzenetricarboxylic acid under ice-cooling and allowed to react at room temperature for 6 to 12 hours, whereby compound C-6 was synthesized.
The structures of the compounds C-1 to C-6 are represented by the following formulas (C-1) to (C-6), respectively.
[ Chemical formula 58]
[ Chemical formula 59]
< Examples and comparative examples >
In each example, the components described in table 1 below were mixed, and each curable resin composition was obtained. In each comparative example, the ingredients described in table 1 below were mixed, and each comparative composition was obtained.
Specifically, the content of the component described in the column other than the "solvent" in table 1 is set to the amount described in "parts by mass" in table 1, and the content of the component described in the column of the "solvent" in table 1 is set to the amount in which the solid content concentration of the composition is the value described in table 1.
The "I-1/I-2" and "80/20" of the "solvent" in Table 1 indicate that the content ratio of I-1 to I-2 is T-1:I-2=80:20 in terms of mass ratio.
The obtained curable resin composition and comparative composition were passed through a polytetrafluoroethylene filter having a pore width of 0.8 μm, and subjected to pressure filtration.
In table 1, the column of "c=c valence" indicates the valence (mmol/g) of the radical polymerizable group derived from the compound having a radical polymerizable group having a molecular weight of 2,000 or less contained in the composition.
In table 1, "-" indicates that the component is not contained.
The details of the components shown in table 1 are as follows.
[ Polymer precursor ]
A-1 to A-6: a-1 to A-6 synthesized in the above
[ Other polymerizable Compound ]
B-1 and B-2: compounds of the structure
[ Chemical formula 60]
[ Specific polymerizable Compound ]
C-1 to C-6: the compounds obtained in the above synthesis examples
[ Photopolymerization initiator ]
D-1 and D-2: compounds of the structure
[ Chemical formula 61]
[ Onium salts or other thermoalciferous agents ]
E-1 to E-3: compounds of the structure
[ Chemical formula 62]
[ Polymerization inhibitor ]
F-1 and F-2: compounds of the structure
F-3: 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., ltd.)
[ Chemical formula 63]
[ Migration inhibitor ]
G-1 and G-2: compounds of the structure
[ Chemical formula 64]
[ Metal adhesion improver ]
H-1 to H-3: compounds of the structure
[ Chemical formula 65]
[ Solvent ]
I-1: gamma-butyrolactone (SANWAYUKA INDUSTRY CORPORATION system)
I-2: dimethyl sulfoxide (FUJIFILM Wako Pure Chemical Corporation system)
I-3: n-methyl-2-pyrrolidone (manufactured by Ashland Co., ltd.)
I-4: ethyl lactate (Tokyo Chemical Industry co., ltd. Manufactured)
[ Other additives ]
J-1: n-phenyl diethanolamine (Tokyo Chemical Industry Co., ltd.)
< Manufacturing of cured film >
In each of examples and comparative examples, a curable resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer on which the above resin layer was formed was dried at 100℃for 4 minutes on a heating plate to give a resin composition layer having a uniform thickness of 20. Mu.m.
The resin composition layer on the silicon wafer was exposed to light at an exposure energy of 400mJ/cm 2 by a broadband exposure machine (UX-1000 SN-EH01, manufactured by USHIO INC.), and the exposed resin composition layer was heated at a temperature rising rate of 5℃per minute under a nitrogen atmosphere, and after reaching 180℃the resin composition layer was heated for 2 hours. The heated resin composition layer and the silicon wafer were immersed in a 3 mass% aqueous solution of hydrofluoric acid, and the heated resin composition layer was peeled from the silicon wafer. The peeled and heated resin composition layer was used as a cured film.
< Evaluation >
In each of examples and comparative examples, the obtained cured films were evaluated for chemical resistance, elongation at break and resolution.
The details of the evaluation method in each evaluation are described below.
[ Resistance to chemicals ]
The obtained cured film 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 cured film 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). The film thickness was measured by an optical film thickness meter (KT-22, manufactured by Footfill Co.).
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in table 2. It can be said that the smaller the dissolution rate value is, the more excellent the chemical resistance of the cured film is.
Evaluation criterion-
A: the dissolution rate was below 250 nm/min.
B: the dissolution rate is 250 nm/min or more and less than 350 nm/min.
C: the dissolution rate is 350 nm/min or more and less than 450 nm/min.
D: the dissolution rate is 450 nm/min or more.
[ Elongation at break ]
The elongation at break of the obtained cured film was measured. The elongation at break of the cured film was measured by a tensile Tester (TENSILON) under conditions of 25℃and 65% RH (relative humidity) in the longitudinal direction and the width direction of the film, with the crosshead speed being 300 mm/min, the sample width being 10mm and the sample length being 50mm, in accordance with JIS-K6251 (Japanese Industrial Specification). The elongation at break was calculated from Eb (%) = (Lb-L0)/L0 (Eb: elongation at break, L0: length of test piece before test, lb: length of test piece when cutting test piece). The elongation at break was measured 10 times each, and an average value (arithmetic average value of the total 10 measured values of elongation at break measured 10 times based on the longitudinal direction) was used for the evaluation.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in table 2. It can be said that the larger the value of the elongation at break, the more excellent the elongation at break of the cured film.
Evaluation criterion-
A: the average value is above 60%
B: the average value is 50% or more and less than 60%
C: the average value is 45% or more and less than 50%
D: the average value is less than 45%
[ Evaluation of lithography (resolution) ]
In each of examples and comparative examples, a curable resin composition or a comparative composition was spin-coated on a silicon wafer to form a resin layer. The silicon wafer on which the resin layer was formed was dried on a hot plate at 100℃for 4 minutes to form a resin composition layer having a uniform film thickness of 20. Mu.m. The resin composition layer on the silicon wafer was exposed by a stepper (Nikon NSR 2005i 9C), and a resin composition layer after exposure was obtained. The exposure was performed by using i-rays, and the exposure amount at 365nm was 400mJ/cm 2. And, exposure was performed using a photomask in which lines and space patterns of 1 μm scale were formed at 5 μm to 25 μm. The resin composition layer after the exposure was developed with cyclopentanone for 60 seconds.
The resin composition layer (line pattern) after the above development was observed with a Scanning Electron Microscope (SEM), and the minimum line width was determined.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in table 2. It can be said that the smaller the minimum line width is, the more excellent the lithography (resolution) is.
Evaluation criterion-
A: minimum line width less than 10 μm
B: a minimum line width of 10 μm or more and less than 20 μm
C: the minimum line width is 20 μm or more or a pattern having edge acuity cannot be obtained.
TABLE 2
Drug resistance Elongation at break Photoetching property
Example 1 B B A
Example 2 B A A
Example 3 A B B
Example 4 A B A
Example 5 A A A
Example 6 A B A
Example 7 B A A
Example 8 B B A
Example 9 A B A
Example 10 B B A
Example 11 A B A
Example 12 A B B
Example 13 A A B
Example 14 A A B
Example 15 A A A
Example 16 A A A
Example 17 A A A
Example 18 A A A
Example 19 A A A
Comparative example 1 D C C
Comparative example 2 D C A
Comparative example 3 C C A
Comparative example 4 D D A
Comparative example 5 C D C
From the above results, it is clear that the cured film obtained from the curable resin composition of the present invention containing the heterocyclic polymer precursor and the specific polymerizable compound 1 and derived from the compound having a radical polymerizable group having a molecular weight of 2,000 or less, which has a radical polymerizable group valence of 0.25 to 4.35mmol/g, or the curable resin composition containing the specific polymerizable compound 2, is excellent in chemical resistance and elongation at break.
The curable resin compositions of comparative examples 1 to 4 did not contain any of the specific polymerizable compound 1 and the specific polymerizable compound 2. It was found that the cured films obtained from the curable resin compositions of comparative examples 1 to 4 had poor chemical resistance.
The curable resin composition of comparative example 5 contained the specific polymerizable compound 1, but the radical polymerizable group valence derived from the compound having a radical polymerizable group having a molecular weight of 2,000 or less was more than 4.35mol/g. It was found that the elongation at break of the cured film obtained from the curable resin composition of comparative example 5 was poor.
< Example 101>
The curable resin composition layer described in example 1 was applied to the surface of a resin substrate having a copper thin layer by spin coating, and dried at 100℃for 5 minutes to form a curable 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 a wavelength of 365nm through a mask (binary mask with a pattern of 1:1 lines and spaces, line width of 10 μm). After exposure, development with cyclopentanone was performed for 30 seconds, and washing with PGMEA was performed for 20 seconds, thereby obtaining a pattern.
Next, the interlayer insulating film for a rewiring layer was formed by heating at 230 ℃ for 3 hours. The interlayer insulating film for a rewiring layer is excellent in insulation properties.
Further, as a result of manufacturing a semiconductor device using these interlayer insulating films for a rewiring layer, normal operation was confirmed.

Claims (17)

1. A curable resin composition comprising:
A polymer precursor which is at least 1 selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and
A polymerizable compound having a hydrogen-bonding nitrogen atom and a group containing 2 or more ethylenically unsaturated groups,
A radical polymerizable group valence of 0.25mmol/g to 4.35mmol/g derived from a compound having a radical polymerizable group having a molecular weight of 2000 or less relative to the total solid content of the composition,
The polymerizable compound comprises a structure A as a structure comprising the hydrogen-bonding nitrogen atom, the structure A is at least 1 structure selected from the group consisting of a urethane bond, a urea bond and an amide bond,
When the polymerizable compound includes a urethane bond as a structure including the hydrogen-bonding nitrogen atom, the polymerizable compound is a compound represented by the following formula (UA-1) or formula (UA-2),
In the case where the polymerizable compound includes a urea bond as a structure including the hydrogen-bonding nitrogen atom, the polymerizable compound is a compound represented by the following formula (UB-1),
In the case where the polymerizable compound includes an amide bond as a structure including the hydrogen-bonding nitrogen atom, the polymerizable compound is a compound represented by the following formula (AM-4) or (AM-5),
In the formula (UA-1) or (UA-2), L A1 represents a hydrocarbon group having a valence of nA, L A2 each independently represents a linking group having a valence of mA+1, R A1 each independently represents a group containing an ethylenically unsaturated group, nA represents an integer of 2 or more, mA represents an integer of 1 or more,
In the formula (UB-1), L B1 represents a hydrocarbon group having a valence of nB, L B2 each independently represents a linking group having a valence of mB+1, R B1 each independently represents a group containing an ethylenically unsaturated group, nB represents an integer of 2 or more, mB represents an integer of 1 or more,
In the above formula (AM-4) or (AM-5), L B1 represents an nB-valent hydrocarbon group, L B2 each independently represents an mB+1-valent linking group, R B1 each independently represents a group containing an ethylenically unsaturated group, nB represents an integer of 2 or more, and mB represents an integer of 1 or more.
2. The curable resin composition according to claim 1, wherein,
The polymerizable compound includes a structure B in which at least 1 bonding site in the structure a is directly bonded to an alkylene group.
3. A curable resin composition comprising:
A polymer precursor which is at least 1 selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; and
A polymerizable compound having a urea bond or an amide bond as a structure containing a hydrogen-bonding nitrogen atom and having a group containing 2 or more ethylenically unsaturated groups,
In the case where the polymerizable compound includes a urea bond as a structure including the hydrogen-bonding nitrogen atom, the polymerizable compound is a compound represented by the following formula (UB-1),
In the case where the polymerizable compound includes an amide bond as a structure including the hydrogen-bonding nitrogen atom, the polymerizable compound is a compound represented by the following formula (AM-4) or (AM-5),
In the formula (UB-1), L B1 represents a hydrocarbon group having a valence of nB, L B2 each independently represents a linking group having a valence of mB+1, R B1 each independently represents a group containing an ethylenically unsaturated group, nB represents an integer of 2 or more, mB represents an integer of 1 or more,
In the above formula (AM-4) or (AM-5), L B1 represents an nB-valent hydrocarbon group, L B2 each independently represents an mB+1-valent linking group, R B1 each independently represents a group containing an ethylenically unsaturated group, nB represents an integer of 2 or more, and mB represents an integer of 1 or more.
4. The curable resin composition according to claim 1 to 3, wherein,
The polymerizable compound contains a (meth) acryloyl group as a group containing the ethylenically unsaturated group.
5. The curable resin composition according to claim 1 to 3, wherein,
The molecular weight of the polymerizable compound is 200 to 1000.
6. The curable resin composition according to any one of claims 1 to 3, further comprising a photo radical polymerization initiator.
7. The curable resin composition according to any one of claims 1 to 3, further comprising an onium salt or a thermal alkaline agent.
8. The curable resin composition according to any one of claims 1 to 3, comprising a polyimide precursor as the polymer precursor.
9. The curable resin composition according to claim 8, wherein,
The polyimide precursor has a repeating unit represented by the following formula (1),
In formula (1), A 1 and A 2 each independently represent an oxygen atom or-NH-, R 111 represents a 2-valent organic group, R 115 represents a 4-valent organic group, and R 113 and R 114 each independently represent a hydrogen atom or a 1-valent organic group.
10. The curable resin composition according to claim 9, wherein,
At least 1 of R 113 and R 114 of formula (1) comprises a free radically polymerizable group.
11. The curable resin composition according to any one of claims 1 to 3, which is used for forming an interlayer insulating film for a rewiring layer.
12. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 11.
13. A laminate comprising 2 or more layers of the cured film of claim 12, wherein any of the cured films comprises a metal layer between each other.
14. A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to any one of claims 1 to 11 to a substrate to form a film.
15. The method for producing a cured film according to claim 14, comprising an exposure step of exposing the film and a development step of developing the film.
16. The method for producing a cured film according to claim 14, comprising a heating step of heating the film at 50 to 450 ℃.
17. A semiconductor device comprising the cured film of claim 12.
CN202080022620.9A 2019-03-22 2020-03-16 Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device Active CN113614130B (en)

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