CN111919172A - Photosensitive resin composition, cured film, laminate, method for producing same, semiconductor device, and thermal alkali generator used for same - Google Patents

Photosensitive resin composition, cured film, laminate, method for producing same, semiconductor device, and thermal alkali generator used for same Download PDF

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CN111919172A
CN111919172A CN201980022753.3A CN201980022753A CN111919172A CN 111919172 A CN111919172 A CN 111919172A CN 201980022753 A CN201980022753 A CN 201980022753A CN 111919172 A CN111919172 A CN 111919172A
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group
resin composition
photosensitive resin
carbon atoms
mass
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井上遥菜
青岛俊荣
福原敏明
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

The invention provides a photosensitive resin composition, a cured film, a laminated body and a manufacturing method thereof, a semiconductor device and a thermal alkali generating agent used in the semiconductor device, wherein the photosensitive resin composition contains a specific thermal alkali generating agent, at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors and a photosensitizer, and the total content of acid groups and acid generating groups contained in the polymer precursors and the photosensitizer is less than 0.5 mmol/g.

Description

Photosensitive resin composition, cured film, laminate, method for producing same, semiconductor device, and thermal alkali generator used for same
Technical Field
The present invention relates to a photosensitive resin composition, a cured film, a laminate, methods for producing the same, a semiconductor device, and a thermoalcogenating agent used for the same.
Background
Polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation properties, and therefore are suitable for various applications (for example, see non-patent documents 1 and 2). The use is not particularly limited, and when a semiconductor device for mounting is taken as an example, the use as a material for an insulating film and a sealing material or a protective film thereof is exemplified. Also, the film is used as a base film, a coating film, or the like of a flexible substrate.
The polyimide resin and the like are generally low in solubility in a solvent. Therefore, a method of dissolving a precursor before cyclization reaction, specifically a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor in a solvent is often used. This makes it possible to realize excellent handling properties and to apply the coating in various forms such as a substrate for processing in the production of each of the above-described products. Thereafter, heating is performed to cyclize the polymer precursor, thereby enabling the formation of a cured product. In addition to high performance such as heat resistance and insulation properties possessed by polyimide resins and the like, the development of industrial applications is expected from the viewpoint of excellent suitability for such production.
There is a resin proposed based on a material as a coating film by utilizing the above characteristics (patent document 1). The photosensitive resin composition contains (A) a polyimide precursor, (B) a specific plasticizer, and (C) a photosensitizer. It is described that a flexible, warp-free, flame-retardant product can be provided.
In order to provide an insulating resin for a rewiring layer, etc., a thermosetting resin composition containing a specific tertiary amine compound and a thermosetting resin cured by alkali cyclization has been proposed (patent document 2). It is described that this enables the cyclization reaction to proceed at a low temperature and has excellent stability. Further, a photosensitive resin composition has been proposed which contains a compound having an anionic portion having a specific quaternary ammonium (cationic portion) and radical initiation energy, a heterocyclic polymer-containing precursor, and a radical polymerizable compound in consideration of being used as an insulating film for a rewiring layer (patent document 3). It is described that this enables the cyclization reaction to proceed at a low temperature and has excellent resolution in exposure and development.
Prior art documents
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-109590
Patent document 2: international publication No. 2015/199220
Patent document 3: japanese patent laid-open publication No. 2016-027357
Non-patent document
Non-patent document 1: science & technology co, ltd. "high functionalization of polyimide in application technology" 2008/4
Non-patent document 2: basis and development of persimmon beng Yaming/Main edition CMC Technical library polyimide material
Disclosure of Invention
Technical problem to be solved by the invention
The above-described technique can provide a photosensitive resin composition which is suitable for an interlayer insulating film, a rewiring layer, and the like, which is cyclized at a low temperature, and which has excellent stability and resolution. On the other hand, since the development speed of semiconductor devices has been further accelerated, improvement of overall performance is strongly demanded from the viewpoint of improvement of some of the enhanced performance. Accordingly, the present invention has been made in view of the use in interlayer insulating films, rewiring layers, and the like, and an object thereof is to provide a photosensitive resin composition which satisfies the performances required for the photosensitive resin composition, i.e., storage stability, mechanical properties, developer solubility in unexposed portions, and photolithography properties, at a high level and is excellent as a whole, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, a semiconductor device, and a thermoalcogenating agent.
Means for solving the technical problem
In view of the above problems, the present inventors have made extensive studies and experiments on a composition containing a polymer precursor, from various viewpoints, such as a formulation and a formula for improving the overall performance, and production conditions. As a result, the present inventors have found that the above problems can be solved by limiting the thermal alkali generator used in combination with the polymer precursor to a specific substance, and have completed the present invention. Specifically, the above object is achieved by the following methods < 1 > and < 2 > - < 23 >.
< 1 > a photosensitive resin composition comprising:
at least one thermal alkali generator selected from the group consisting of a thermal alkali generator represented by the following formula (B1) and a thermal alkali generator represented by the following formula (B2);
at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors; and
a light-sensitive agent,
the total content of the acid group and the acid generating group contained in the polymer precursor and the sensitizer is 0.5mmol/g or less.
[ chemical formula 1]
Figure BDA0002704034780000031
In the formulae (B1) and (B2), R1、R2And R3Each independently is an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom, wherein R is1And R2Not simultaneously being a hydrogen atom, and R1、R2And R3Has no carboxyl group.
< 2 > the photosensitive resin composition according to the above < 1 >, wherein the alkali generation temperature of the thermal alkali generator is 120 ℃ or more and 200 ℃ or less.
< 3 > the photosensitive resin composition according to the above < 1 > or < 2 >, wherein the above thermal base generator has a pKa of more than 7.
< 4 > the photosensitive resin composition according to any one of < 1 > - < 3 >, wherein the polymer precursor comprises a polyimide precursor.
< 5 > the photosensitive resin composition according to < 4 > wherein the above polyimide precursor is represented by the following formula (1);
[ chemical formula 2]
Figure BDA0002704034780000032
In the formula (1), A1And A2Each independently represents an oxygen atom or NH, R111Represents a 2-valent organic group, R115Represents a 4-valent organic group, R113And R114Each independently represents a hydrogen atom or a 1-valent organic group.
< 6 > the photosensitive resin composition according to any one of < 1 > to < 5 >, wherein the molar absorption coefficient of the thermal alkali generator at a wavelength of 365nm is 100l/(mol cm) or less.
< 7 > the photosensitive resin composition according to any one of < 1 > to < 6 >, wherein the thermal base generator contains a thermal base generator that generates a base having a conjugate acid pKa of 10 or more by heating.
< 8 > the photosensitive resin composition according to any one of < 1 > to < 7 >, wherein the above-mentioned photosensitizer contains a photopolymerization initiator.
< 9 > the photosensitive resin composition according to any one of < 1 > to < 8 > for use in development using a developer containing 90 mass% or more of an organic solvent.
< 10 > the photosensitive resin composition according to any one of < 1 > -9 > for use in forming an interlayer insulating film for a rewiring layer.
< 11 > a cured film obtained by curing the photosensitive resin composition described in any one of < 1 > -to < 10 >.
< 12 > or < 11 > of the cured film, wherein the film thickness is 1 to 30 μm.
< 13 > a laminate having 2 or more layers of the cured film < 11 > or < 12 >.
< 14 > a laminate having < 11 > or < 12 > of the above-mentioned 3 to 7 cured films.
< 15 > the laminate according to < 13 > or < 14 > having a metal layer between the above cured films.
< 16 > A method for producing a cured film, which comprises a film-forming step of applying the photosensitive resin composition of any one of < 1 > -to < 10 > to a substrate to form a film.
< 17 > the method of producing a cured film according to < 16 > comprising an exposure step of exposing the film to light and a development step of developing the film.
< 18 > the method of < 17 >, wherein the developing solution used in the above-mentioned development contains 90 mass% or more of an organic solvent.
< 19 > the method for producing a cured film according to any one of < 16 > to < 18 >, which comprises a step of heating the film at 80 to 450 ℃.
< 20 > A method for producing a laminate, which comprises conducting the method for producing a cured film described in any one of < 16 > to < 19 > a plurality of times.
< 21 > a semiconductor device having the cured film of < 11 > or < 12 > or the laminate of any one of < 13 > - < 15 >.
< 22 > a thermal alkali-producing agent represented by the following formula (B1) or formula (B2);
[ chemical formula 3]
Figure BDA0002704034780000051
In the formulae (B1), (B2), R1、R2And R3Each independently is an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom, wherein R is1And R2Not simultaneously being a hydrogen atom, and R1、R2And R3Has no carboxyl group.
< 23 > the thermal alkali generator < 22 > is used for a photosensitive resin composition which is developed using a developer containing 90 mass% or more of an organic solvent.
Effects of the invention
The photosensitive resin composition of the present invention is required to be used for an interlayer insulating film, a rewiring layer, or the like, and is generally excellent in storage stability, mechanical properties, developer solubility at unexposed portions, and photolithography. Also provided are a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, a semiconductor device, and a thermoalcogenating agent, each using the photosensitive resin composition.
Detailed Description
The present invention will be described in detail below. In the present specification, "to" is used in the sense of including numerical values described before and after the lower limit value and the upper limit value.
The following description of the constituent elements of the present invention may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
As for the labeling of the group (atomic group) in the present specification, a label not recorded as substituted and unsubstituted includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" is not particularly limited, and in addition to exposure using light, drawing using a particle beam such as an electron beam or an ion beam is also included in exposure. Examples of the light used for exposure include active light such as far ultraviolet light, extreme ultraviolet light (EUV light), X-ray, and electron beam, which are typically represented by a bright line spectrum of a mercury lamp or an excimer laser, and radiation.
In the present specification, "(meth) acrylate" means two or 1 of "acrylate" and "methacrylate", "meth (acrylic acid)" means two or 1 of "acrylic acid" and "methacrylic acid", and "(meth) acryl" means two or 1 of "acryl" and "methacryl".
In the present specification, the term "step" is not limited to an independent step, and is also included in the present term as long as an intended action of the step can be achieved even when the step cannot be clearly distinguished from other steps.
In the present specification, the solid content means a mass percentage of other components than the solvent with respect to the total mass of the composition. The temperature in the present specification is 23 ℃ unless otherwise specified.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as styrene 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 determined, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, the eluent was measured with THF (tetrahydrofuran). Unless otherwise stated, the detection is performed by a 254nm wavelength detector using UV rays (ultraviolet rays).
The photosensitive resin composition of the present invention (hereinafter, may be simply referred to as "the composition of the present invention" or "the resin composition of the present invention") is characterized by containing at least one thermal base generator (hereinafter, may be referred to as "specific thermal base generator") selected from the group consisting of a thermal base generator represented by the formula (B1) and a thermal base generator represented by the formula (B2), at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a photosensitizer, wherein the total content of acid groups and acid generating groups contained in the polymer precursor and the photosensitizer (hereinafter, may be referred to as "the amount of acid groups and the like") is 0.5mmol/g or less. By adopting this structure, a photosensitive resin composition having excellent storage stability, mechanical properties, developer solubility in unexposed portions, and photolithography properties as a whole can be obtained. The reason for solving the above problem, including estimation, is as follows.
In the photosensitive resin composition, the amount of an acid group or the like contained in a polymer precursor or the like is reduced, whereby a material that can be more rapidly developed in an organic solvent having a low polarity can be provided. A thermosetting film formed from a photosensitive resin composition that can be developed with an organic solvent generally has low moisture absorption, and is excellent in adhesion to a substrate and device reliability. On the other hand, since the amount of an acid group or the like in a polymer precursor or the like is small, if a basic compound is present in the composition, a cyclization reaction of the polymer precursor is easily advanced. This results in a decrease in storage stability. In the present invention, by using a specific thermal alkali generator having a structure which is substantially neutral before thermal decomposition and generates an alkali after thermal decomposition, the photosensitive resin composition can be stably stored while maintaining good curability by heating the polymer precursor contained in the photosensitive resin composition. Further, the specific thermal alkali generator is preferably nonionic, and thus the resin composition can be further excellent in the organic solvent developability.
< specific thermal alkali-producing agent >
The photosensitive resin composition of the present invention contains a thermal alkali generator (specific thermal alkali generator) represented by formula (B1) or formula (B2).
[ chemical formula 4]
Figure BDA0002704034780000071
In the formulae (B1), (B2), R1、R2And R3Each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. Wherein R is1And R2Not simultaneously hydrogen atoms. And, R1、R2And R3Has no carboxyl group.
In the present specification, the tertiary amine structure refers to a structure in which 3 bonds of a nitrogen atom having a valence of 3 are all covalently bonded to a carbon atom of a hydrocarbon system. Therefore, when the bonded carbon atom is a carbon atom representing a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, the carbon atom is not limited thereto. In the present invention, the organic group contained in the specific thermal alkali generator does not have a tertiary amine structure, and therefore, when the resist solution is stored, amidation reaction of the polymer in the solution is suppressed, and the storage stability of the resist solution is excellent. Further, since each substituent has no carboxyl group, the solubility in an organic solvent is excellent, and the developability is excellent.
In the formulae (B1) and (B2), R is preferable1、R2And R3At least 1 of these comprises a cyclic structure, more preferably at least 2 comprise a cyclic structure. The cyclic structure may be any 1 of monocyclic ring and fused ring, and is preferably monocyclic or fused ring having 2 condensed monocyclic rings. Monocyclic rings are preferably 5-or 6-membered rings, preferably 6-membered rings. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring. By including the cyclic structure in this manner, the solubility in an organic solvent becomes high, and the basic property and boiling point of the amine generated by thermal decomposition are high, and therefore the amidation reaction of the polymer is more effectively promoted.
More specifically, R1And R2Preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms). These groups may have a substituent T described later in a range in which the effects of the present invention are exerted. R1And R2The ring may be bonded to each other to form a ring. The ring to be formed is preferably a 4-to 7-membered nitrogen-containing heterocycle. R1And R2In particular, a linear or branched alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms) which may have a substituent T is preferable, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms) which may have a substituent T is more preferable, and a cyclohexyl group which may have a substituent T is even more preferable.
As R3Examples thereof include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, further preferably 8 to 16 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms) or an arylalkoxy group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 12). Among them, preferred are cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms), aralkenyl groups, and arylalkoxy groups. R3The substituent T may be further substituted within a range in which the effects of the present invention are exhibited.
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
[ chemical formula 5]
Figure BDA0002704034780000081
In the formula, R11And R12And R31And R32Are respectively reacted with R in the formula (B1)1And R2The same is true.
R13The group may have a substituent T in a range where the effects of the present invention are exhibited, such as an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 12 carbon atoms). Wherein R is13Preferably an arylalkyl group.
R33And R34Each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12, more preferably 1 to 8, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12, more preferably 2 to 8, further preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 10 carbon atoms), an arylalkyl group (preferably 7 to 23, more preferably 7 to 19, further preferably 7 to 11 carbon atoms), preferably a hydrogen atom.
R35The aromatic polyester resin composition is preferably an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), and an aryl group.
The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1 a).
[ chemical formula 6]
Figure BDA0002704034780000091
R11And R12Is defined as in formula (B1-1) with R11And R12The same definition is applied.
R15And R16The alkyl group is preferably a hydrogen atom, an alkyl group (preferably a carbon number of 1 to 12, more preferably 1 to 6, further preferably 1 to 3), an alkenyl group (preferably a carbon number of 2 to 12, more preferably 2 to 6, further preferably 2 to 3), an aryl group (preferably a carbon number of 6 to 22, more preferably 6 to 18, further preferably 6 to 10), an arylalkyl group (preferably a carbon number of 7 to 23, more preferably 7 to 19, further preferably 7 to 11), and preferably a hydrogen atom or a methyl group.
R17Is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an aryl group (preferably having 3 carbon atoms)6 to 22, more preferably 6 to 18, further preferably 6 to 12), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, further preferably 7 to 12), and an aryl group is particularly preferred.
The molecular weight of the specific thermal base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more. The molecular weight of the specific thermal alkali generator is in the above range, and thus the solubility in the organic solvent is excellent and the developability is not deteriorated. Moreover, the decomposed product after thermal decomposition is not likely to remain in the thermosetting film, and the reliability of the device is not impaired.
The alkali generation temperature of the specific heat alkali generator is preferably 120 ℃ to 200 ℃, more preferably 130 ℃ to 180 ℃, and still more preferably 140 ℃ to 170 ℃. By controlling the temperature, curing based on cyclization of the polymer precursor can be more reliably promoted. The alkali generation temperature can be measured as described in examples below.
The difference between the base generation temperature of the specific thermal base generator and the maximum temperature at the time of heating for cyclizing the polymer precursor (maximum temperature-base generation temperature) is preferably 5 ℃ to 100 ℃, more preferably 10 ℃ to 80 ℃, and still more preferably 15 ℃ to 60 ℃. Depending on whether or not the range is such, the mechanical properties are further improved.
The pKa of the conjugate acid of the base generated by heating the specific thermal base generator is preferably 10 or more, more preferably 11 or more, and still more preferably 12 or more. The upper limit is actually 15 or less. This basic group is strong, and thus the curability of the polymer precursor is more effective.
The pKa of the specific thermal base generator is preferably greater than 7, more preferably 8 or more, and further preferably 9 or more. The upper limit is actually 12 or less. Since the pKa is set to the above range, the basic property of the thermal alkali generator during storage is weakened, and the polymer precursor is not cured, so that the stability thereof is further improved.
The specific thermal base generator preferably comprises neutral molecules. Neutral refers to electrically neutral, preferably a base that is not formed from an anion or cation. The atoms in the molecule are linked by covalent bonding, and a compound having a total valence of zero is preferable.
The method for measuring pka can be measured according to the method described in the examples below.
The molar absorption coefficient of the specific thermobase generator contained in the photosensitive resin composition used in the present invention at a wavelength of 365nm is preferably 500l/(mol · cm) or less, more preferably 300l/(mol · cm) or less, and still more preferably 100l/(mol · cm) or less. The lower limit is actually 50 l/(mol. cm) or more. UV-2600 (manufactured by Shimadzu Corporation) was used as a device for measuring molar absorptivity. The measurement was performed on 3 samples, and the results were arithmetically averaged. Other details follow JISK 0115: 2004 (Japanese Industrial Standard). In the present invention, the thermal alkali generator is preferably one in which the absorption of light (i-ray) at a wavelength of 365nm is suppressed to a low level as described above. This makes it possible to realize more excellent mechanical properties without deteriorating the light transmittance and the photolithography property at the time of exposure.
The substituent T includes an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms), an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), a hydroxyalkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), a heteroaryl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms), and examples of a heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom, an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms), and, A hydroxyl group, a primary or secondary amino group (the number of carbon atoms may be 0 to 24, or 0 to 12, or 0 to 6), a quaternary ammonium group (the number of carbon atoms may be 3 to 24, or 3 to 12, or 3 to 6), a thiol group, an acyl group (preferably the number of carbon atoms is 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3), an acyloxy group (preferably the number of carbon atoms is 2 to 12), an acrylic acid ester, a vinyl aromatic compoundA number of 2 to 12, more preferably 2 to 6, even more preferably 2 to 3), an aroyl group (preferably 7 to 23, more preferably 7 to 19, even more preferably 7 to 11), an aroyloxy group (preferably 7 to 23, more preferably 7 to 19, even more preferably 7 to 11), a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxo group (═ O), an imino group (which may be ═ NH), an alkylene group (═ C (R) s)N)2) And the like. A hetero atom may be interposed between the alkylene chains of the substituent T. The alkyl group, alkenyl group, aryl group, and arylalkyl group of the substituent T may be further substituted with another substituent.
RNIs a hydrogen atom or an organic group. The organic group is preferably an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 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), or an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms).
Examples of the specific thermal alkali-producing agent include the compounds shown in the examples.
In the photosensitive resin composition, the content of the specific thermal alkali generator in the solid content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less.
The amount is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, and still more preferably 0.5 part by mass or more, per 100 parts by mass of the polymer precursor. The upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less.
When the amount is within the above range, the action of the specific thermal alkali generator can be sufficiently exerted, and the amount of the residue of the thermal decomposition product can be suppressed to such an extent that the reliability of the device is not affected.
One or more specific thermal alkali generators may be used. When a plurality of such compounds are used, the total amount thereof falls within the above range.
The specific thermal alkali-producing agent may be used in combination with or without other thermal alkali-producing agents.
In one embodiment of the present invention, the content of the specific thermal base generator in the photosensitive resin composition of the present invention is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 99% by mass or more.
< Polymer precursor >
The photosensitive resin composition of the present invention contains at least 1 polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors. The total content of acid groups and acid generating groups contained in the polymer precursor is preferably 0.5mmol/g or less. The polymer precursor is more preferably a polyimide precursor, and still more preferably a polyimide precursor containing a structural unit represented by the following formula (1).
Polyimide precursor
The polyimide precursor preferably contains a structural unit represented by the following formula (1). By adopting such a structure, a composition having more excellent film strength can be obtained.
[ chemical formula 7]
Figure BDA0002704034780000121
A1And A2Each independently represents an oxygen atom or NH, R111Represents a 2-valent organic group, R115Represents a 4-valent organic group, R113And R114Each independently represents a hydrogen atom or a 1-valent organic group. -C (═ O) -a1-R114and-C (═ O) -A2-R113Each of these groups is preferably a group having no acid group or acid generating group.
A1And A2Each independently an oxygen atom or NH, preferably an oxygen atom.
R111Represents an organic group having a valence of 2. Examples of the 2-valent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, an aromatic heterocyclic group, and a group containing a combination of these groups, and 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, or a group containing a combination of these groups, and more preferably an aromatic group having 6 to 20 carbon atoms.
R111Preferably derived from diamines. The diamine used in the production of the polyimide precursor includes linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One diamine may be used alone, or two or more diamines may be used.
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 combination thereof, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following.
[ chemical formula 8]
Figure BDA0002704034780000131
In the formula, A is preferably a single bond or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C (═ O) -, -S-, -S (═ O)2-, -NHCO-and combinations thereof, more preferably a single bond or a group selected from C1-3 alkylene groups which may be substituted with fluorine atoms, -O-, -C (-O) -, -S-and-SO2The group of (E) is further preferably selected from the group consisting of-CH2-、-O-、-S-、-SO2-、-C(CF3)2-and-C (CH)3)2-a 2-valent radical of the group consisting.
Specific examples of the diamine include those selected from the group consisting of 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-or 1, 4-diaminocyclohexane, 1, 2-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4 ' -diaminobiphenyl and 3,3 ' -diaminobiphenyl, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylmethane and 3,3 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl sulfone and 3,3 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl sulfide and 3,3 ' -diaminodiphenyl sulfide, 4 ' -diaminobenzophenone and 3,3 ' -diaminobenzophenone, 3 ' -dimethyl-4, 4 ' -diaminobiphenyl, 2 ' -dimethyl-4, 4 ' -diaminobiphenyl, (4,4 ' -diamino-2, 2-dimethylbiphenyl), 3 ' -dimethoxy-4, 4 ' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4 ' -diamino-terphenyl, p-phenylene, 4,4 '-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, 4,4 ' -diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3 ', 4,4 ' -tetraaminobiphenyl, 3 ', 4,4 ' -tetraaminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4 ' -diaminobiphenyl, 9 ' -bis (4-aminophenyl) fluorene, 4,4 ' -dimethyl-3, 3 ' -diaminodiphenylsulfone, 3 ', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane, ethyl 2- (3 ', 5' -diaminobenzoyloxy) acrylate, 2, 4-diaminocumene and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, 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) tetradecafluoroheptane, 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, a salt thereof, a pharmaceutically acceptable carrier, and a pharmaceutically acceptable carrier, 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', 5,5 '-tetramethyl-4, 4' -diaminobiphenyl, 4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2 ', 5, 5', 6,6 '-hexafluorotolidine, and 4, 4' -diaminotetrabiphenyl.
Also, diamines (DA-1) to (DA-18) shown below are also preferable.
[ chemical formula 9]
Figure BDA0002704034780000151
Further, as a preferable example, a diamine having at least 2 or more alkylene glycol units in the main chain can be cited. The diamine is preferably a diamine containing 1 or two ethylene glycol chains and propylene glycol chains of 2 or more in total in 1 molecule, and more preferably 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 (see above: product name, manufactured by HUNTSMAN), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, but the present invention is not limited thereto.
The following shows the structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176.
[ chemical formula 10]
Figure BDA0002704034780000161
In the above, x, y and z are average values.
From the viewpoint of flexibility of the obtained cured film, R111Preferably represented by-Ar0-L0-Ar0-represents. Wherein Ar is0Each independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L is0Represents 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-, -S (═ O)2-, -NHCO-and a group selected from these combinations. The definition of the preferred range is the same as that of A in AR-8 described above.
From the viewpoint of i-ray transmittance, R111Preferred is a 2-valent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and ready availability, the 2-valent organic group represented by formula (61) is more preferable.
[ chemical formula 11]
Figure BDA0002704034780000162
R50～R57Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R50～R57At least 1 of which is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.
As R50～R57Examples of the 1-valent organic group 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 12]
Figure BDA0002704034780000171
R58And R59Each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.
Examples of the diamine compound to which the structure of formula (51) or (61) is imparted include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4, 4' -diaminooctafluorobiphenyl. One of these may be used, or two or more of these may be used in combination.
R in the formula (1)115Represents a 4-valent organic group. The organic group having a valence of 4 is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).
[ chemical formula 13]
Figure BDA0002704034780000172
R112The definition of (b) is the same as that of A in AR-8, and the preferable range is also the same.
With respect to R in the formula (1)115Specific examples of the 4-valent organic group include tetracarboxylic acid residues remaining after removal of the acid dianhydride group from the tetracarboxylic acid dianhydride. FourthlyThe carboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
[ chemical formula 14]
Figure BDA0002704034780000173
R115Represents a 4-valent organic group. R115Is defined as in formula (1) and R115The same definition is applied.
Specific examples of the tetracarboxylic acid dianhydride include those selected from the group consisting of pyromellitic acid, pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfide tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylmethane tetracarboxylic acid dianhydride, 2 ', 3,3 ' -diphenylmethane tetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic acid dianhydride, 2,3,3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 4,4 ' -oxydiphthalic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 1,4,5, 7-naphthalenetetracarboxylic acid dianhydride, and mixtures thereof, 2, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 3,4, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,8,9, 10-phenanthrenetetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, and at least one of alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.
Preferred examples thereof include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.
[ chemical formula 15]
Figure BDA0002704034780000181
R in the formula (1)113And R114Each independently represents a hydrogen atom or a 1-valent organic group. Preferably R113And R114At least 1 of them contains a radical polymerizable group, and more preferably 2 contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, (meth) acryloyl group, a group represented by the following formula (III), and the like.
[ chemical formula 16]
Figure BDA0002704034780000191
In the formula (III), R200Represents a hydrogen atom or a methyl group, and more preferably a methyl group.
In the formula (III), R201An alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2Or a (poly) oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms; the number of repetitions is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms). In addition, the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Preferred R201Examples of (3) include vinyl, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene and-CH2CH(OH)CH2-, more preferably vinyl, propylene, trimethylene, -CH2CH(OH)CH2-。
Particularly preferably R200Is methyl, R201Is a vinyl group.
From the viewpoint of solubility in an organic solvent, R113Or R114Preferably a 1-valent organic group. As the 1-valent organic group, a group containing a linear or branched alkyl group, a ring or the like is preferredThe alkyl group and the aromatic group are preferably substituted with an aromatic group.
The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic group). The alkyl group may be any 1 of linear, branched and cyclic. Examples of the straight-chain or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, bornyl, camphylenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecyl, camphoroyl, dicyclohexyl, and sterenyl. Among these, cyclohexyl is most preferable from the viewpoint of achieving high sensitivity. The alkyl group substituted with an aromatic group is preferably a straight-chain alkyl group substituted with an aromatic group described later.
Examples of the aromatic group include an aromatic hydrocarbon group and an aromatic heterocyclic group.
Specific examples of the aromatic hydrocarbon group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene (pentalene) ring, indene ring, azulene ring, heptalene (heptalene) ring, indacene ring, perylene ring, condensed pentacene ring, ethylnaphthalene (acenaphhthene) ring, phenanthrene ring, anthracene ring, condensed tetraphenyl ring, pentalene (pentalene) ring,
Figure BDA0002704034780000202
a (chrysene) ring, a triphenylene ring, a fluorene ring, a biphenyl ring, or the like having an aromatic hydrocarbon ring.
Examples of the aromatic heterocyclic group include groups having an aromatic heterocyclic ring such as a substituted or unsubstituted pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine (quinolizine) ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline (quinolazoline) ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline (phenanthroline) ring, thiene ring, chromene (chromene) ring, xanthene (xanthene) ring, phenoxathiine (phenoxathiine) ring, phenothiazine (phenothiazine) ring or phenazine (phenoxazine) ring.
The polyimide precursor also preferably has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not specifically defined, but is actually 50% by mass or less.
Further, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by formula (1) for the purpose of improving adhesion to the substrate. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
Preferably, the structural unit represented by formula (1) is a structural unit represented by formula (1-A).
[ chemical formula 17]
Figure BDA0002704034780000201
A1、A2、R111、R113And R114Are each independently defined as A in the formula (1)1、A2、R111、R113And R114The same definition is applied to preferred ranges. R112And R in the formula (5)112The definitions are the same, and the preferred ranges are the same.
In the polyimide precursor, the structural unit represented by formula (1) may be one kind, or two or more kinds. Further, the structural isomer of the structural unit represented by the formula (1) may be contained. The polyimide precursor may contain other types of structural units in addition to the structural unit of formula (1).
An embodiment of the polyimide precursor of the present invention is exemplified by a polyimide precursor in which 50 mol% or more, more preferably 70 mol% or more, and particularly 90 mol% or more of the total structural units are structural units represented by formula (1). The upper limit is actually 100 mol% or less.
The polyimide precursor preferably has a weight average molecular weight (Mw) of 2000 to 500000, more preferably 5000 to 100000, and still more preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and further preferably 4000 to 25000.
The dispersion degree of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.
The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted 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 one kind or two or more kinds.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.
The production of the polyimide precursor preferably includes a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, whereby solid deposition can be performed.
Precursor of polybenzoxazole
The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).
[ chemical formula 18]
Figure BDA0002704034780000211
R121Represents a 2-valent organic group, R122Represents a 4-valent organic group, R123And R124Are respectively independentAnd (b) represents a hydrogen atom or a 1-valent organic group.
R121Represents an organic group having a valence of 2. The organic group having a valence of 2 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, and particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms). As a constituent R121As the aromatic group (2), R in the above formula (1) is exemplified111Examples of (3). The aliphatic group is preferably a straight chain aliphatic group. R121Preferably from 4, 4' -oxodibenzoyl chloride.
In the formula (2), R122Represents a 4-valent organic group. As the 4-valent organic group, the same as defined for R in the above formula (1)115The definitions are the same, and the preferred ranges are the same. R122Preferably from 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R123And R124Each independently represents a hydrogen atom or a 1-valent organic group, which is as defined above for R in the formula (1)113And R114The same definition is applied to preferred ranges. preferably-OR124and-OR123Are groups that do not have acid groups and acid generating groups, respectively.
The polybenzoxazole precursor may contain other kinds of structural units in addition to the structural unit of the above formula (2).
From the viewpoint of suppressing the warp of the cured film caused by the dead cycle, it is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit.
[ chemical formula 19]
Figure BDA0002704034780000221
Z has a structure a and a structure b, R1sIs 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), R2sIs a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 6 carbon atoms)1 to 3 carbon atoms), R3s、R4s、R5s、R6sAt least 1 of them is an aromatic group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and particularly preferably having 6 to 10 carbon atoms), and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably having 1 to 18 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 to 6 carbon atoms), and may be the same or different. The polymerization of the a structure and the b structure may be a block polymerization or a random polymerization. In the Z portion, the a structure is preferably 5 to 95 mol%, the b structure is preferably 95 to 5 mol%, and a + b is preferably 100 mol%.
In the formula (SL), preferable Z is R in the structure of b5sAnd R6sZ being phenyl. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and 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 elastic modulus of the polybenzoxazole precursor after the dehydration dead cycle can be reduced, and the effects of suppressing warpage and improving solubility can be achieved at the same time.
The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and further preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and further preferably 4000 to 25000.
The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.
The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more, based on the total solid content of the composition. The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, still more preferably 95% by mass or less, and still more preferably 95% by mass or less, based on the total solid content of the composition.
The photosensitive resin composition of the present invention may contain one kind of polymer precursor, or may contain two or more kinds. When two or more are contained, the total amount is preferably within the above range.
< solvent >
The photosensitive 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 preferred 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, -caprolactone, -valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.) (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc, Ethyl 2-oxobutyrate, and the like.
Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
As the aromatic hydrocarbons, for example, preferable aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
Preferred sulfoxides include dimethyl sulfoxide.
Preferable examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.
The solvent is preferably a mixture of two or more types from the viewpoint of improvement of the coating surface shape and the like.
In the present invention, it is preferable that the solvent composition comprises one solvent or a mixture of two or more solvents selected from the group consisting of methyl 3-ethoxypropionate, ethyl ethylcellosolve 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. Particularly preferably, dimethyl sulfoxide and γ -butyrolactone are used simultaneously.
From the viewpoint of coatability, the content of the solvent is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass, of the total solid content concentration of the photosensitive resin composition of the present invention. The content of the solvent may be adjusted according to the desired thickness and coating method.
The solvent may contain only one kind, or may contain two or more kinds. When two or more solvents are contained, the total amount thereof is preferably in the above range.
< photosensitizer >
In the present invention, the photosensitive resin composition contains a photosensitizer. The total content of the acid group and the acid generating group contained in the photosensitizer is preferably 0.5mmol/g or less. Examples of the photosensitizer include a photopolymerization initiator, a photocuring accelerator, and a sensitizing dye.
In the present invention, the total amount of the sensitizer is preferably 1 to 10% by mass of the photosensitive resin composition. The photosensitizer is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80 to 100% by mass of a photopolymerization initiator.
[ photopolymerization initiator ]
The photosensitive resin composition used in the present invention may contain a photopolymerization initiator. The photopolymerization initiator is preferably a photo radical polymerization initiator.
The photo radical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light from an ultraviolet region to a visible region is preferable. Also, the active agent may be one that exerts some action with a photo-excited sensitizer and generates active radicals.
The photo radical polymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 mol in a range of about 300 to 800nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferable to perform the measurement at a concentration of 0.01g/L by using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian corporation).
The photosensitive resin composition of the present invention contains a photo radical polymerization initiator, and thus can be applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then cured by radicals generated by irradiation with light, thereby reducing the solubility in a light irradiated portion. Therefore, for example, there is an advantage that regions having different solubilities can be easily produced according to the electrode pattern by exposing the photosensitive resin composition layer through a photomask having a pattern for shielding only the electrode portion.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole 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 may be made to the descriptions in paragraphs 0165 to 0182 of japanese patent application laid-open No. 2016-027357, which are incorporated herein by reference.
Examples of the ketone compound include the compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, which are incorporated herein by reference. Among commercially available products, KAYACURE DETX (Nippon Kayaku co., ltd.) is also preferably used.
As the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese patent No. 4225898 can be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184(IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: both manufactured by BASF Corp.) were used.
As the aminoacetophenone initiator, commercially available IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade name: manufactured by BASF) were used.
As the aminoacetophenone-based initiator, a compound described in Japanese patent laid-open publication No. 2009-191179, which has a maximum absorption wavelength matching a light source having a wavelength of 365nm or 405nm, can also be used.
Examples of the acylphosphine initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 or IRGACURE-TPO (trade name: manufactured by BASF) can be used as a commercially available product.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF corporation).
The photo radical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be further effectively improved. Among oxime compounds, oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a curing accelerator.
Specific examples of the oxime compound include compounds described in Japanese patent application laid-open Nos. 2001-233842, 2000-080068, and 2006-342166.
Preferred examples of the oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the photosensitive resin composition of the present invention, an oxime compound (oxime-based photopolymerization initiator) is preferably used as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > C — N — O — C (═ O) -in the molecule.
[ chemical formula 20]
Figure BDA0002704034780000271
Among commercially available products, IRGACURE OXE01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF Co., Ltd.), and ADEKA OPTOMER N-1919 (photo radical polymerization initiator 2 described in ADEKA CORPORATION, Japanese patent application laid-open No. 2012 and 014052) can also be preferably used. Also, TR-PBG-304 (manufactured by Changzhou powerful electronic New Material Co., Ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Also, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.
Further, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24 and 36 to 40 described in section 0345 of Japanese patent application laid-open No. 2014-500852, and the compound (C-3) described in section 0101 of Japanese patent application laid-open No. 2013-164471.
As the most preferable oxime compound, an oxime compound having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and an oxime compound having a thioaryl group as shown in Japanese patent laid-open No. 2009-191061 are exemplified.
From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal 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, and 3-aryl-substituted coumarin compounds.
More preferred photo radical polymerization initiators are trihalomethyl triazine compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, further preferably at least one compound selected from the group consisting of trihalomethyl triazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, still further preferably metallocene compounds or oxime compounds are used, and still further preferably oxime compounds are used.
Further, as the photo radical polymerization initiator, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone such as benzophenone and N, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propane-1, quinones such as alkylanthraquinone which are condensed with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal can be used. Further, a compound represented by the following formula (I) can also be used.
[ chemical formula 21]
Figure BDA0002704034780000281
In the formula (I), RI00Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group substituted with at least 1 of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group, RI01Is a group represented by the formula (II), or is a group represented by the formula (II) with RI00Same radicals, RI02～RI04Each independently is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.
[ chemical formula 22]
Figure BDA0002704034780000291
In the formula, RI05～RI07With R of the above formula (I)I02～RI04The same is true.
Further, as the photo radical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International publication No. 2015/125469 can be used.
When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The photopolymerization initiator may contain only one kind, or may contain two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.
(photo-curing accelerator)
The photosensitive resin composition used in the present invention may contain a photo-curing accelerator. The photo-curing accelerator in the present invention is preferably a photo-curing accelerator (photobase generator) which generates a base by exposure, and is a photo-curing accelerator which does not exhibit activity under ordinary conditions at normal temperature and normal pressure, but generates a base (basic substance) particularly preferably when irradiation of electromagnetic waves is performed as an external stimulus. The base generated by exposure functions as a catalyst when the polymer precursor is cured by heating, and therefore can be preferably employed.
In the present invention, a known photo-curing accelerator can be used as the photo-curing accelerator. Examples of the compound include ionic compounds in which a base component is neutralized by forming a base, such as transition metal compound complexes, compounds having a structure of ammonium salts and the like, and substances in which a base is formed by an amidine moiety and a carboxylic acid to be latent, and nonionic compounds in which a base component is latent by urethane bond, oxime bond and the like, such as urethane derivatives, oxime ester derivatives, and acyl compounds.
Examples of the photocuring accelerator of the present invention include a photocuring accelerator having a cinnamamide structure as disclosed in japanese patent laid-open publication No. 2009-080452 and international publication No. 2009/123122, a photocuring accelerator having a urethane structure as disclosed in japanese patent laid-open publication nos. 2006-189591 and 2008-247747, and a photocuring accelerator having an oxime structure or a carbamoyloxime structure as disclosed in japanese patent laid-open publication nos. 2007-249013 and 2008-003581, but the present invention is not limited thereto, and a known photocuring accelerator may be used in addition to these.
Examples of the photo-curing accelerator include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of Japanese patent laid-open No. 2012-093746, compounds described in paragraphs 0022 to 0069 of Japanese patent laid-open No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese patent laid-open No. 2013-204019, and compounds described in paragraph 0052 of International publication No. 2010/064631.
As commercially available products of the photo-curing accelerator, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can be used.
When the photo-curing accelerator is used, the content of the photo-curing accelerator in the composition is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less.
One or two or more of the photocuring accelerators can be used. When two or more kinds are used, the total amount is preferably within the above range.
Sensitizing pigment
The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active ray to become an electron excited state. The sensitizing dye in an electron excited state is brought into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and functions such as electron transfer, energy transfer, heat generation, and the like are generated. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed. The details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The sensitizing pigment may be used alone or in combination of two or more.
< thermal radical polymerization initiator >
The photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator within a range not departing from the gist of the present invention.
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, the polymerization reaction of the polymer precursor can be carried out together with the cyclization of the polymer precursor, and therefore, 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. 2008-063554.
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, based on the total solid content of the photosensitive resin composition of the present invention. The thermal radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more thermal radical polymerization initiators are contained, the total amount thereof is preferably in the above range.
< polymerizable Compound >
< radically polymerizable compound >
The photosensitive resin composition of the present invention preferably contains a radical polymerizable compound.
As the radical polymerizable compound, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinylphenyl group, a vinyl group, a (meth) acryloyl group, and an allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.
The number of radical polymerizable groups of the radical polymerizable compound may be 1 or 2 or more, but the radical polymerizable compound preferably has 2 or more radical polymerizable groups, and more preferably 3 or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.
The molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 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 photosensitive resin composition of the present invention preferably contains at least one 2-or more-functional radical polymerizable compound containing 2 or more polymerizable groups, and more preferably contains at least one 3-or more-functional radical polymerizable compound. Further, a mixture of a 2-functional radical polymerizable compound and a 3-or more-functional radical polymerizable compound may be used. The number of functional groups of the radically polymerizable compound means the number of radically polymerizable groups in 1 molecule.
Specific examples of the radical polymerizable compound include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), an ester thereof, and an amide thereof, and preferably an ester of an unsaturated carboxylic acid and a polyol compound and an amide of an unsaturated carboxylic acid and a polyamine compound. Further, addition reaction products of unsaturated carboxylic acid esters or amides having an affinity substituent such as a hydroxyl group, an amino group, or a mercapto group with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, and the like can also be preferably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having releasable substituent groups such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferable. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like can be used. As a specific example, reference can be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent laid-open No. 2016-027357, which are incorporated herein by reference.
The radical polymerizable monomer is also preferably a compound having a boiling point of 100 ℃ or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resulting mixture, JP-B-48-041708, JP-B-50-006034, carbamates of (meth) acrylic acid disclosed in JP-B-51-037193, esters of (meth) acrylic acid, and mixtures thereof, The polyester acrylates described in JP-A-48-064183, JP-A-49-043191 and JP-A-52-030490, and the polyfunctional acrylates or methacrylates such as epoxy acrylates as a reaction product of an epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also suitable. Further, there can be mentioned a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate.
Further, as a preferable radical polymerizable compound other than the above, compounds having a fluorene ring and having 2 or more ethylenically unsaturated bond-containing groups or cardo (cardo) resins described in japanese patent application laid-open nos. 2010-160418, 2010-129825, and 4364216 can be used.
Further, as other examples, specific unsaturated compounds described in Japanese patent publication No. 46-043946, Japanese patent publication No. 1-040337, and Japanese patent publication No. 1-040336, vinylphosphonic acid-based compounds described in Japanese patent publication No. 2-025493, and the like can be cited. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, those described as photopolymerizable monomers and oligomers in "Journal of the addition 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 can be preferably used, and these contents are incorporated in the present specification.
Further, the following 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.
Further, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can be used as other radical polymerizable compounds, and these contents are incorporated in the present specification.
Preferred examples of the radical polymerizable compound include dipentaerythritol triacrylate (commercially available product is KAYARAD-330; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol tetraacrylate (commercially available product is KAYARAD-320; Nippon Kayaku Co., manufactured by Ltd., A-TMMT: Shin-Nakamura Chemical Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (commercially available product is KAYARAD-310; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product is KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd., A-DPH; Shin-Nakamura Chemical Co., manufactured by Ltd.), and a structure in which a (meth) acryloyl group thereof is bonded via an ethylene glycol residue or a propylene glycol residue. Their oligomer type can also be used.
Commercially available products of the radical polymerizable compound include, for example, SR-494 (manufactured by Sartomer Company, Inc.) which is a 4-functional acrylate having 4 vinyloxy chains, SR-209, 231, 239 (manufactured by Sartomer Company, Inc.) which is a 2-functional acrylate having 4 vinyloxy chains, DPCA-60 (manufactured by Ltd.) which is a 6-functional acrylate having 6 oxypentylene chains, TPA-330 (manufactured by Ltd.) which is a 3-functional acrylate having 3 isobutenoxy chains, urethane oligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., manufactured by Ltd.), NK ester M-40G, NK (ester M-4G, NK), NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Co., Ltd.), DPHA-40 kH (manufactured by Chemicals Co., Ltd.), Nippon-306 H., UA-306T, UA-306I, AH-600, T-600, AI-600(Kyoeisha chemical Co., Ltd.), BLEMMER PME400(NOF corporation.) and the like.
As the radical polymerizable compound, urethane acrylates such as those disclosed in JP-B-48-041708, JP-B-51-037193, JP-B-2-032293 and JP-B-2-016765, urethane compounds having an ethylene oxide skeleton as disclosed in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also preferable. Further, as the radical polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 1-105238 can be used.
The photosensitive 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 due to 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, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate. The monofunctional radical polymerizable compound is preferably a compound having a boiling point of 100 ℃ or higher under normal pressure in order to suppress volatilization before exposure.
(ii) polymerizable compound other than the above radical polymerizable compound
The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the radical polymerizable compound. Examples of the polymerizable compound other than the radical polymerizable compound include compounds having a methylol group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine compound.
(Compound having hydroxymethyl group, alkoxymethyl group or acyloxymethyl group)
The compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group is preferably a compound represented by the following formula (AM1), (AM4) or (AM 5).
[ chemical formula 23]
Figure BDA0002704034780000341
(wherein t represents an integer of 1 to 20, R104Represents a t-valent organic group having 1 to 200 carbon atoms, R105Is represented by-OR106or-OCO-R107A group represented by R106R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms107Represents an organic group having 1 to 10 carbon atoms. )
[ chemical formula 24]
Figure BDA0002704034780000351
(in the formula, R404Represents a 2-valent organic group having 1 to 200 carbon atoms, R405Is represented by-OR406or-OCO-R407A group represented by R406R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms407Represents an organic group having 1 to 10 carbon atoms. )
[ chemical formula 25]
Figure BDA0002704034780000352
(wherein u represents an integer of 3 to 8, R504Represents a u-valent organic group having 1 to 200 carbon atoms, R505Is represented by-OR506Or, -OCO-R507A group represented by R506R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms507Represents an organic group having 1 to 10 carbon atoms. )
Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBISOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2, 6-dimethylymethyl-4-t-butylcresol), 2,6-dimethoxymethyl-p-cresol, 2, 6-diacetoxymethyl-4-t-butylcresol (2, 6-dimethyloxymethyl-cresol-p-dimethylcresol-2, 6-diacetoxymethyl-cresol-2, 6-dimethylcresol-p-cresol-tolylcresol (trade name, 2, 6-dimethyloxymethyl-p-cresol-p-tolylcresol-p-cresol-p-e-p-, 2, 6-diacetoxymethylethyl-p-cresol), and the like.
Specific examples of the compound represented by the formulｃA (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORATION), NIKALAMX-280, NIKALAC MX-270, and NIKALAC MW-100LM (trade name, manufactured by SanwｃA Chemical Co., Ltd.).
(epoxy Compound (Compound having epoxy group))
The epoxy compound is preferably a compound having 2 or more epoxy groups in 1 molecule. The epoxy group undergoes a crosslinking reaction at 200 ℃ or lower, and it is difficult to cause shrinkage of the film since a dehydration reaction resulting from crosslinking is not caused. Therefore, by containing the epoxy compound, low-temperature curing and warpage of the composition can be effectively suppressed.
The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and preferably 2 to 15.
Examples of the epoxy compound include, but are not limited to, bisphenol a type epoxy resins, bisphenol F type epoxy resins, alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether, epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, and the like. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-. Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppression of warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E preferably contain a polyethylene oxide group.
(Oxetane Compound (Compound having an Oxetanyl group))
Examples of the oxetane compound include a compound having 2 or more oxetane rings in 1 molecule, 3-ethyl-3-hydroxymethoxyoxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexylmethyl) oxetane, and 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester. As a specific example, TOAGOSEI co, a series of ARON oxoetane (for example, OXT-121, OXT-221, OXT-191, and OXT-223) made by ltd can be preferably used, and these may be used alone or two or more kinds may be used in combination.
(benzoxazine Compound (Compound having benzoxazolyl group))
The benzoxazine compound is preferable because degassing does not occur during curing due to a crosslinking reaction resulting from a ring-opening addition reaction, and further, generation of warpage is suppressed by reducing thermal shrinkage.
Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (hereinafter, trade name: Shikoku Chemicals Corporation), benzoxazine adduct of polyhydroxystyrene resin, and novolak type dihydrobenzoxazine compound. These may be used alone, or two or more kinds may be used in combination.
When the polymerizable compound is contained, the content thereof is preferably more than 0 mass% and 60 mass% or less with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and still more preferably 30% by mass or less.
The polymerizable compound may be used alone or in combination of two or more. When two or more kinds are used simultaneously, the total amount is preferably within the above range.
< migration inhibitor >
The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively inhibit the metal ions from the metal layer (metal wiring) from migrating into the photosensitive resin composition layer.
The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (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, and triazine ring), compounds having a thiourea group and a mercapto group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
Further, an ion scavenger that scavenges anions such as halogen ions can also be used.
As other migration inhibitors, there can be used rust inhibitors described in paragraph 0094 of Japanese patent application laid-open No. 2013-015701, compounds described in paragraphs 0073-0076 of Japanese patent application laid-open No. 2009-283711, compounds described in paragraph 0052 of Japanese patent application laid-open No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese patent application laid-open No. 2012-194520, and the like.
Specific examples of the migration inhibitor include the following compounds.
[ chemical formula 26]
Figure BDA0002704034780000381
When the photosensitive resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of the photosensitive resin composition.
The migration inhibitor may be one kind alone, or two or more kinds thereof. When the number of migration inhibitors is two or more, the total amount thereof is preferably in the above range.
< polymerization inhibitor >
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycoletherdiamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 5-hydroxy-quinoline, and the like can be preferably used, 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-tert-butyl) phenylmethane and the like. Further, the polymerization inhibitor described in paragraph 0060 of Japanese patent laid-open publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication No. 2015/125469 can also be used.
Further, the following compound (Me is methyl) can also be used.
[ chemical formula 27]
Figure BDA0002704034780000382
When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.05 to 2.5% by mass, based on the total solid content of the photosensitive resin composition of the present invention.
The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is two or more, the total amount thereof is preferably in the above range.
< modifier for improving adhesion of Metal >
The photosensitive resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to a metal material used for an electrode, a wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent.
Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and compounds described in paragraphs 0055 of International publication No. 2014/097594. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.
[ chemical formula 28]
Figure BDA0002704034780000391
The metal adhesion improver can also be a compound described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 or a sulfide described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935.
The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polymer precursor. When the lower limit value is set to the upper limit value or more, the adhesion between the cured film and the metal layer after the curing step is good, and when the upper limit value is set to the lower limit value or less, the heat resistance and the mechanical properties of the cured film after the curing step are good. The metal adhesion improver may be one kind only, or two or more kinds. When two or more kinds are used, the total amount thereof is preferably in the above range.
< other additives >
The photosensitive resin composition of the present invention may contain, as necessary, various additives such as 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, and an aggregation inhibitor, as long as the effects of the present invention are not impaired. When these additives are added, the total amount added is preferably 3% by mass or less of the solid content of the composition.
Chain transfer agent
The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in The third edition of The Polymer dictionary (The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. These radicals can be generated by supplying hydrogen to a low-activity radical to generate a radical, or by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, and the like) can be preferably used.
When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 1 to 5% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The chain transfer agent may be one kind or two or more kinds. When the number of the chain transfer agents is two or more, the total range is preferably the above range.
Surface active agent
Various surfactants may be added to the photosensitive resin composition of the present invention in order to improve coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. Also, the following surfactants are also preferable.
[ chemical formula 29]
Figure BDA0002704034780000411
When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The surfactant may be one kind only, or two or more kinds. When the number of the surfactants is two or more, the total range is preferably in the above range.
Higher fatty acid derivatives
In order to prevent inhibition of polymerization by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the photosensitive resin composition of the present invention so as to be locally present on the surface of the composition during drying after application.
When the photosensitive 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 based on the total solid content of the photosensitive resin composition of the present invention. The higher fatty acid derivative may be one kind or two or more kinds. When the number of the higher fatty acid derivatives is two or more, the total range is preferably within the above range.
< restrictions on other substances included >
From the viewpoint of coating surface shape, the moisture content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass.
The metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulation properties. 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.
As a method for reducing metal impurities inadvertently contained in the photosensitive resin composition of the present invention, there can be mentioned a method in which a raw material having a small metal content is selected as a raw material constituting the photosensitive resin composition of the present invention, the raw material constituting the photosensitive resin composition of the present invention is filtered through a filter, and the inside of the apparatus is lined with polytetrafluoroethylene and distilled under conditions in which contamination is suppressed as much as possible.
In view of the use as a semiconductor material, the content of the halogen atom in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and still more preferably less than 200 mass ppm, from the viewpoint of corrosion of wiring. Among these, the substance present in the state of the halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably in the above-mentioned range.
As the container for the photosensitive resin composition of the present invention, a conventionally known container can be used. Further, for the purpose of suppressing the contamination of impurities into the raw material or the composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. Examples of such a container include those described in Japanese patent laid-open publication No. 2015-123351.
< preparation of the composition >
The photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
For the purpose of removing foreign matter such as dust and fine particles in the composition, filtration using a filter is preferably performed. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one previously 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 sizes or different materials may be used in combination. Also, various materials may be filtered multiple times. When the filtration is performed a plurality of times, it may be a circulation filtration. Further, the filtration may be performed after the pressurization. When filtration is performed after pressurization, the pressurization is preferably performed at a pressure of 0.05MPa to 0.3 MPa.
In addition to filtration using a filter, an 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.
In the present invention, the total content of the acid groups and the acid-generating groups (amount of acid groups [ Sigma Ac ]) contained in the polymer precursor and the photosensitizer in the photosensitive resin composition is 0.5mmol/g or less. The acid group in the present specification is a group having 4 or less pKa, and carboxylic acids and sulfonic acids are exemplified. The acid generating group in the present specification is a group which can generate an acid group in a liquid of a photosensitive resin composition or a film obtained from the photosensitive resin composition by a process using the photosensitive resin composition such as heating or exposure, and examples thereof include a group in which the acid group is protected by a releasing force.
The amount of the acid group or the like in the photosensitive resin composition of the present invention is more preferably 0.4mmol/g or less, still more preferably 0.3mmol/g or less, and still more preferably 0.2mmol/g or less. The lower limit value is actually 0.01mmol/g or more. In the present invention, since the amount of the acid group or the like is suppressed to a low level, favorable development can be performed by an organic solvent without the aid of an alkaline solution. Further, it is presumed that the resin composition in patent document 1 is alkali-soluble, and therefore the amount of acid groups or the like in (for example, [0064]), the resin or the like exceeds 2.0 mmol/g.
< cured film, laminate, semiconductor device, and method for producing same
Next, the cured film, the laminate, the semiconductor device, and methods for manufacturing these will be described.
The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The thickness of the cured film of the present invention can be set to, 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 two or more layers to form a laminate, and further, may be laminated in 3 to 7 layers to form a laminate. The laminate of the cured films of the present invention having two or more layers is preferably a laminate having a metal layer between the cured films. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.
The cured film of the present invention can also be used for manufacturing a printing plate such as an offset printing plate or a screen printing plate, for etching a molded member, for manufacturing a protective varnish or a dielectric layer in electronics, particularly microelectronics, and the like.
The method for producing a cured film of the present invention includes the case where the photosensitive resin composition of the present invention is used. Specifically, the method comprises a film forming step (layer forming step) of applying the photosensitive resin composition of the present invention to a substrate to form a film, and a heating step of heating the photosensitive resin composition in a layer form at 80 to 450 ℃ (preferably at 80 to 350 ℃). The method for producing the cured film preferably includes the following steps: an exposure step of exposing the film after the film formation step (layer formation step); and a developing step of developing the exposed photosensitive resin composition layer (film, i.e., resin layer). After the development, a heating step of heating (preferably at 80 to 450 ℃) (more preferably at 80 to 350 ℃) is included, whereby the exposed resin layer can be further cured. In addition, when the photosensitive resin composition is used as described above, the composition is cured by exposure in advance, and then, if necessary, a desired process (for example, lamination described below) is performed, whereby the composition can be further cured by heating.
The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present invention, in the case where the cured film is formed and then the film formation step (layer formation step) and the heating step of the photosensitive resin composition are further performed again or the photosensitivity is imparted, it is preferable to perform the film formation step (layer formation step), the exposure step, and the development step (further heating step as necessary) in this order. In particular, it is preferable to sequentially perform each step a plurality of times (2 layers or more) or 3 to 7 times (i.e., 3 to 7 layers). By laminating the cured films in this manner, a laminate can be produced. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film or between the cured films or between both of them.
These will be described in detail below.
< film formation step (layer formation step) >)
The production method according to a preferred embodiment of the present invention includes a film formation step (layer formation step) of applying the photosensitive resin composition to a substrate to form a film (layer).
The type of the substrate may be appropriately determined depending On the application, and is not particularly limited to a semiconductor substrate such as silicon, silicon nitride, polysilicon, silicon oxide, or amorphous silicon, a quartz substrate, Glass substrate, an optical film, a ceramic material, a vapor-deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, paper substrate, SOG (Spin On Glass), a TFT (thin film transistor) array substrate, an electrode plate of a plasma display device (PDP), or the like. In the present invention, a semiconductor substrate is particularly preferable, and a silicon substrate is more preferable.
When the photosensitive 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 substrate.
The method of applying the photosensitive resin composition to a substrate is preferably coating.
Specifically, examples of suitable methods include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and an ink jet method. From the viewpoint of uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected depending on the shape of the substrate, and a spin coating method, a spray coating method, an ink jet method, or the like is preferable if the substrate is a circular substrate such as a wafer, and a slit coating method, a spray coating method, an ink jet method, or the like is preferable if the substrate is a rectangular substrate. In the case of spin coating, for example, the coating can be applied at a rotation speed of 500 to 2000rpm for about 10 seconds to 1 minute.
(drying process)
The production method of the present invention may further include a step of drying the photosensitive resin composition layer after the film formation step (layer formation step) to remove the solvent. The preferable drying temperature is 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably 90 to 110 ℃. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
Exposure process
The production method of the present invention may further include an exposure step of exposing the photosensitive resin composition layer. The exposure amount is not particularly limited as long as the photosensitive resin composition can be cured, and is preferably 100 to 10000mJ/cm in terms of exposure energy at a wavelength of 365nm2More preferably, the irradiation is 200 to 8000mJ/cm2。
The exposure wavelength can be suitably determined in the range of 190 to 1000nm, and is preferably 240 to 550 nm.
As the exposure wavelength, in relation to the light source, there can be mentioned (1) a semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (three wavelengths of g, h, i-ray), (4) an excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), and (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, and the like. The photosensitive resin composition of the present invention is particularly preferably exposed to light by a high-pressure mercury lamp, and particularly preferably exposed to light by i-ray. Thereby, particularly high exposure sensitivity can be obtained.
Development process
The production method of the present invention may include a developing step of performing a developing treatment on the exposed photosensitive resin composition layer. Development is performed, thereby removing an unexposed portion (unexposed portion). The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as coating, spraying, dipping, or ultrasonic waves can be used.
The development is performed using a developer. The developer can be used without particular limitation as long as the unexposed portion (unexposed portion) can be removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90 mass% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be determined as a calculated value by inputting the structural formula by ChemBioDraw.
Examples of the organic solvent include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, -caprolactone, -valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.) (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.; examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellulose 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; and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.; and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferably cited; dimethyl sulfoxide is preferably used as the sulfoxide.
In the present invention, cyclopentanone and γ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
The developer preferably contains an organic solvent in an amount of 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. The developer may be 100 mass% of an organic solvent.
The developer is preferably a non-alkaline developer. From this viewpoint, it is preferable that the developer mainly containing the organic solvent does not contain an alkali compound. For example, as described in [0064] of patent document 1, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, or the like can be removed from a preferable developer applied to the present invention.
The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during development is not particularly limited, and the development can be usually carried out at 20 to 40 ℃.
The treatment with the developer may be followed by further rinsing. Preferably, the rinsing is performed using a solvent different from the developer. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.
Heating process
The production method of the present invention preferably includes a film formation step (layer formation step), a drying step, or a step of heating after the development step. In the heating step, a cyclization reaction of the polymer precursor proceeds. The composition of the present invention may contain a radical polymerizable compound other than a polymer precursor, but curing of an unreacted radical polymerizable compound other than a polymer precursor and the like may 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, further preferably 140 ℃ or higher, further preferably 160 ℃ or higher, and further preferably 170 ℃ or higher. The upper limit is preferably 500 ℃ or lower, more preferably 450 ℃ or lower, still more preferably 350 ℃ or lower, yet more preferably 250 ℃ or lower, and yet more preferably 220 ℃ or lower.
The heating is preferably performed at a temperature rise rate of 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and even more preferably 3 to 10 ℃/min from the start of heating to the maximum heating temperature. By setting the temperature rise rate to 1 ℃/min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the temperature rise rate to 12 ℃/min or less, it is possible to relax the residual stress of the cured film.
The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, and still more preferably 25 to 120 ℃. The temperature at the start of heating is the temperature at the start of the heating step to the maximum heating temperature. For example, when the photosensitive resin composition is dried after being applied to a substrate, the temperature of the film (layer) after drying is preferably gradually increased from a temperature 30 to 200 ℃ lower than the boiling point of the solvent contained in the photosensitive resin composition.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
In particular, when a multilayer laminate is formed, the heating temperature is preferably 180 to 320 ℃, and more preferably 180 to 260 ℃, from the viewpoint of adhesion between the layers of the cured film. The reason for this is not clear, but it is considered that the ethynyl groups of the polymer precursors between the layers are crosslinked with each other by setting the temperature to this temperature.
The heating may be performed in stages. As an example, for example, the following pretreatment steps may be performed: the temperature is raised from 25 ℃ to 180 ℃ at 3 ℃/min, maintained at 180 ℃ for 60 minutes, from 180 ℃ to 200 ℃ at 2 ℃/min, and maintained at 200 ℃ for 120 minutes. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, as described in U.S. Pat. No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. By such a pretreatment step, the properties of the film can be improved. The pretreatment step may be performed for a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be carried out in 2 stages or more, for example, the pretreatment step 1 is carried out at a temperature of 100 to 150 ℃ and the pretreatment step 2 is carried out at a temperature of 150 to 200 ℃.
Further, the heating and the cooling may be performed, and the cooling rate at this time is preferably 1 to 5 ℃/min.
From the viewpoint of preventing the decomposition of the polymer precursor, it is preferable to perform the heating step in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon. The oxygen concentration is preferably 50ppm (by volume) or less, more preferably 20ppm (by volume) 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 photosensitive resin composition layer after the development treatment.
The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper.
The method for forming the metal layer is not particularly limited, and a conventional method can be employed. For example, the methods described in Japanese patent laid-open Nos. 2007-157879, 2001-521288, 2004-214501 and 2004-101850 can be used. For example, photolithography, lift-off, electro-plating, electroless plating, etching, printing, a method of combining these, and the like are considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electroplating can be cited.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, based on the thickest part.
Lamination process
The production method of the present invention preferably further comprises a lamination step.
The laminating step is a series of steps of performing the film forming step (layer forming step) and the heating step again on the surface of the cured film (resin layer) or the metal layer, or performing the film forming step (layer forming step), the exposure step, and the development treatment step in the photosensitive resin composition in this order. Of course, the laminating step may include the drying step and the heating step.
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. The surface activation treatment is exemplified by plasma treatment.
The laminating step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.
For example, the resin layer has a structure of preferably 3 to 7 layers, and more preferably 3 to 5 layers, as in the case of resin layer/metal layer/resin layer/metal layer.
That is, in the present invention, it is particularly preferable that after the metal layer is provided, the photosensitive resin composition is further subjected to a film formation step (layer formation step) and a heating step for covering the metal layer, or the photosensitive resin composition is subjected to the film formation step (layer formation step), the exposure step, and the development treatment step (heating step is further performed as necessary) in this order. The photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step.
The invention also discloses a semiconductor device having the cured film or the laminate of the invention. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer, reference can be made to the descriptions of paragraphs 0213 to 0218 of japanese patent application laid-open No. 2016-027357 and the description of fig. 1, and the contents thereof are incorporated in the present specification.
Further, patterning of a sealing film, a substrate material (an undercoat film, a coating film, and an interlayer insulating film of a flexible printed circuit board), or an insulating film for mounting as described above may be performed by etching or the like. For these applications, for example, reference can be made to Science & technology co, ltd, "high functionalization and application technology of polyimide" 4 months 2008, kaki benayi ming/main edition, base and development of CMC Technical library "polyimide material" 11 months 2011 release, japan polyimide aromatic polymer research institute/edition "latest polyimide base and application" NTS Inc, 8 months 2010, and the like.
Examples
The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the processing steps, and the like, which are described in the following examples, can be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. "part" and "%" are based on mass unless otherwise specified.
< Synthesis of Polymer precursor (resin) >
< Synthesis example 1 >
[ Synthesis of polyimide precursor A-1 derived from 4,4 '-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4, 4' -diaminodiphenyl ether ]
A diester of 4,4 '-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate was produced by mixing 21.2g of 4, 4' -oxydiphthalic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine, 1mg of water, and 250mL of diglyme, and stirring at 60 ℃ for 4 hours. The water content of the obtained reaction solution was measured and found to be 133 mass ppm. Followed byThe reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃2. After diluting with 50mL of N-methylpyrrolidone, a solution prepared by dissolving 25.1g of 4, 4' -diaminodiphenyl ether in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and after stirring the mixture for 2 hours, 20mL of ethanol was added. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380g of tetrahydrofuran. The obtained solution was precipitated in 6 liters of water to obtain a polyimide precursor, filtered, and dried at 45 ℃ for 3 days under reduced pressure to obtain a polyimide precursor as a solid powder. The weight-average molecular weight of the polyimide precursor A-1 was 23300, and the number-average molecular weight was 9600.
< Synthesis example 2 >
[ Synthesis of polyimide precursor A-2 derived from 4, 4' -oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a) shown below ]
A diester of 4,4 '-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate was produced by mixing 21.2g of 4, 4' -oxydiphthalic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine, 1mg of water, and 250mL of diglyme (diethylene glycol dimethyl ether) and stirring at 60 ℃ for 4 hours. The water content of the obtained reaction solution was measured and found to be 120 mass ppm. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃2. After diluting with 50mL of N-methylpyrrolidone, a solution obtained by dissolving 38.0g of the hydroxyl group-containing diamine (a) shown below in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 2 hours, followed by addition of 20mL of ethanol. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380g of tetrahydrofuran. The obtained solution was precipitated in 6 liters of water to obtain a polyimide precursor, filtered, and dried at 45 ℃ for 3 days under reduced pressure to obtain a polyimide precursor as a solid powder. The weight-average molecular weight of the polyimide precursor A-2 was 29400, the number-average molecular weight was 10800, and the acid value was 5.6 mgKOH/g.
Diamine (a)
[ chemical formula 30]
Figure BDA0002704034780000511
< Synthesis example 3 >
[ Synthesis of polyimide precursor A-3 derived from 4,4 '-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4, 4' -diaminodiphenyl ether ]
A diester of 4,4 '-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate was produced by mixing 21.2g of 4, 4' -oxydiphthalic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine, 1mg of water, and 250mL of diglyme, and stirring at 60 ℃ for 4 hours. The water content of the obtained reaction solution was measured, and found to contain 1450 mass ppm. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃2. After diluting with 50mL of N-methylpyrrolidone, a solution prepared by dissolving 25.1g of 4, 4' -diaminodiphenyl ether in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and after stirring the mixture for 2 hours, 20mL of ethanol was added. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380g of tetrahydrofuran. The obtained solution was precipitated in 6 liters of water to obtain a polyimide precursor, filtered, and dried at 45 ℃ for 3 days under reduced pressure to obtain a polyimide precursor as a solid powder. The weight average molecular weight of the polyimide precursor A-3 was 22000, and the number average molecular weight was 10000.
< Synthesis example 4 >
[ Synthesis of polyimide precursor composition A-4 derived from 4,4 '-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4, 4' -diaminodiphenyl ether ]
42.4g of 4, 4' -oxydiphthalic anhydride, 36.4g of 2-hydroxyethyl methacrylate, 22.07g of pyridine and 100mL of tetrahydrofuran were mixed and stirred at 60 ℃ for 4 hours. Subsequently, the reaction mixture was cooled to-10 ℃, a solution in which 34.35g of diisopropylcarbodiimide was dissolved in 80mL of γ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at-10. + -. 5 ℃, and the mixture was stirred for 30 minutes. Next, a solution of 25.1g of 4, 4' -diaminodiphenyl ether dissolved in 200mL of gamma-butyrolactone was added dropwise to the reaction mixture over 60 minutes at-10. + -. 5 ℃ and the mixture was stirred for 1 hour. The precipitate generated in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. The obtained reaction solution was precipitated into 14L of water to obtain a polyimide precursor, which was then filtered and dried under reduced pressure at 45 ℃ for 2 days. The obtained powdery polyimide precursor a-4 had a weight average molecular weight of 23800 and a number average molecular weight of 8700.
< Synthesis example 5 >
[ Synthesis of polybenzoxazole precursor A-5 derived from 4,4 '-carbonyldibenzoic acid, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane and methacryloyl chloride ]
18.5g of 4, 4' -carbonyldibenzoic acid and 250mL of N-methylpyrrolidone were mixed. Next, the reaction mixture was cooled to-10 ℃ and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10. + -. 5 ℃2. Subsequently, a solution of 21.0g of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane dissolved in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10. + -. 5 ℃ over 60 minutes, and the mixture was stirred for 2 hours. Next, to the obtained reaction solution, 9.3g of triethylamine was added in an ice-cooled state, 12.0g of methacryloyl chloride was added dropwise, and further stirred in an ice-cooled state for 2 hours, thereby obtaining a solution containing a polybenzoxazole precursor. Then, at 6 litersThe polybenzoxazole precursor was precipitated in water and the water-polybenzoxazole precursor mixture was stirred at 5000rpm for 15 minutes. The solid polybenzoxazole precursor was filtered and dissolved in 380g of tetrahydrofuran. The resulting solution was added to 6 liters of water, the polybenzoxazole precursor was precipitated, and the water-polybenzoxazole precursor mixture was stirred at 5000rpm for 15 minutes. The solid of polybenzoxazole precursor was filtered again and dried at 45 c under reduced pressure for 3 days. The polybenzoxazole precursor A-5 had a weight average molecular weight of 28,900 and a number average molecular weight of 8,800. The ratio of components having a molecular weight of 1,000 or less was 0.3% by mass.
< preparation of photosensitive resin composition >
A coating solution of a photosensitive resin composition was prepared by mixing a polymer precursor with the components shown in table 1 below to obtain a uniform solution. Each photosensitive resin composition was passed through a filter made of ADVANTEC co, LTD having a pore width of 0.8 μm, and pressure-filtered.
< temperature at which base is generated >
3.0mg of the polymer precursor was weighed, and the temperature decreased by 5% by mass when the temperature was raised to 500 ℃ at a temperature raising rate of 20 ℃/min was measured as the alkali generation temperature from the thermal alkali generator by TGA (TA Instruments, model Q500). The pKa of the conjugate acid of the generated base was determined by identifying the decomposition species by LC-MS and calculating the pKa of the structure of the conjugate acid of the obtained decomposition species using the following software package. Software package: advanced Chemistry Development (ACD/Labs) software V8.14 supports the Solaris system (1994-2007ACD/Labs)
< amount of acid group, etc. >
The total content of the acid group and the acid generator (amount of acid group, etc.; Σ Ac [ mmol/g ]) in the photosensitizer was measured by NMR (nuclear magnetic resonance) for each of the photosensitive resin compositions in examples and comparative examples.
< storage stability >
Each photosensitive resin composition was left at room temperature (25 ℃ C.), and the storage stability was evaluated until precipitates could be visually confirmed.
A: no precipitation was observed over 2 weeks.
B: precipitation was observed within 1 week and 2 weeks.
C: precipitation was observed within 1 week.
D: incompatibilities were found at the preparation stage.
< mechanical Property (tensile Strength) >
Each photosensitive resin composition was applied to a silicon wafer by a spin coating method, thereby forming a photosensitive resin composition layer. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ℃ for 4 minutes to obtain a photosensitive resin composition layer having a uniform thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed at 400mJ/cm using a broad-band exposure machine (manufactured by USHIO INC., UX-1000SN-EH01)2The exposed photosensitive resin composition layer (resin layer) was heated at a temperature rise rate of 5 ℃/min under a nitrogen atmosphere to 230 ℃ and then heated for 3 hours. The cured resin layer was immersed in a 3% hydrofluoric acid solution to peel the resin layer from the silicon wafer, thereby obtaining a resin film.
The resin film peeled from the silicon wafer was subjected to a tensile strength test. In the test, a tensile tester (Tensilon) was used to measure the cross-head speed at 300 mm/min, the width at 10mm and the sample length at 50mm in the longitudinal and width directions of the film under an environment of 25 ℃ and 65% RH (relative humidity) in accordance with JIS-K6251 (Japanese Industrial Standard). For the evaluation, the breaking elongation at 10 times of cutting was measured and the average value thereof was used. The results were evaluated by distinguishing them as follows.
A: over 60 percent
B: more than 50 percent and less than 60 percent
C: less than 50 percent
< solubility of developer in unexposed part >
Each photosensitive resin composition was applied to a silicon wafer by spin coating. The silicon wafer to which the photosensitive resin composition was applied was heated with a hot plate at 100 ℃ for 4 minutes to obtain photosensitive resin composition layers each having a thickness of 20 μm. The photosensitive resin composition layer was immersed in cyclopentanone at 23 ℃ and the time required for complete dissolution was measured, from which the dissolution rate was calculated. In the test, a resist development analyzer (RDA-790 EB manufactured by Litho Tech Japan Corporation) was used. The results were evaluated by distinguishing them as follows.
A: 0.55 μm/sec or more
B: 0.4 μm/sec or more and less than 0.55 μm/sec
C: less than 0.4 μm/sec
< photoetching property >
Each photosensitive resin composition was applied to a silicon wafer by spin coating. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100 ℃ for 4 minutes to form a photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005i 9C). The exposure was carried out with i-rays at a wavelength of 365nm and at 200, 300, 400, 500, 600, 700, 800mJ/cm2The exposure energy was varied from 5 μm to 25 μm, and exposure was performed using a photomask of 1 μm increment of line and space.
The exposed photosensitive resin composition layer was subjected to negative development using cyclopentanone for 60 seconds. The smaller the line width of the obtained photosensitive resin composition layer (pattern), the larger the difference in solubility in the developer between the light-irradiated portion and the light-non-irradiated portion, which is a preferable result. Further, a small change in the line width with respect to a change in the exposure energy indicates a large exposure latitude, which is a preferable result. The limit of measurement was 5 μm. The results were evaluated by distinguishing them as follows.
A: less than 10 μm
B: more than 10 μm and 20 μm or less
C: patterns exceeding 20 μm or having a line width with edge sharpness cannot be obtained.
Figure BDA0002704034780000551
< photopolymerization initiator (photosensitizer) >
IRGACURE OXE01 (trade name) manufactured by BASF corporation
IRGACURE784 (trade name) manufactured by BASF corporation
IRGACURE OXE01/IRGACURE784 (trade name) manufactured by BASF corporation
Mixing ratio 1/1 (quality ratio)
E, Sigma Ac: the total content [ mmol/g ] of acid groups and acid-generating groups in the polymer precursor and the sensitizer
< radical polymerizable Compound (polymerizable Compound) >)
SR-209 (trade name) [ 2-functional ] ArKema S.A. product
A-TMMT (trade name) [ 4-functional ] Shin Nakamura Chemical Co., Ltd., manufactured by Ltd
DPHA (trade name) [ 6-functional ] Nippon Kayaku Co., Ltd
< solvent >
NMP (N-methylpyrrolidone)/ethyl lactate
BGL (gamma-butyrolactone)/DMSO (dimethyl sulfoxide)
Mixing ratio 200/100 (quality ratio)
< thermal alkali production agent >
[ chemical formula 31]
Figure BDA0002704034780000561
TGB1：
pKa32, base generation temperature 180 ℃, pKa11.4 of the conjugate acid of the generated base, molar absorptivity of 40 l/(mol. cm)
TGB2：
pKa4, base generation temperature 150 ℃, pKa5.1 of the conjugate acid of the generated base, molar absorptivity 0 l/(mol. cm)
TGB3：
pKa30, base generation temperature 200 ℃, pKa11.4 of the conjugate acid of the generated base, molar absorption coefficient 20 l/(mol. cm)
TGB4：
pKa16.2, base generation temperature 170 ℃, pKa11.4 of conjugate acid of generated base, molar absorptivity 10l/(mol cm)
TGB5：
pKa30, base generation temperature 160 ℃, pKa9 of conjugate acid of generated base, molar absorptivity 0 l/(mol. cm)
TGB6：
pKa32, base generation temperature 190 ℃, pKa10.4 of the conjugate acid of the generated base, molar absorptivity 0 l/(mol. cm)
From the above results, it is understood that the photosensitive resin composition of the present invention using a specific thermoalcogenating agent exhibits good results (B or more) in storage stability, mechanical properties, developer solubility in unexposed portions, and photolithography, and it is understood that the photosensitive resin composition is excellent as a whole. On the other hand, when a thermal alkali generator (TBG2) having a tertiary amine structure and a carboxyl group was used (comparative example 1), the storage stability was poor. If the thermal alkali generator is not used (comparative example 2), the mechanical properties are poor. When a polymer precursor having a high acid value is used (comparative example 3), storage stability, developer solubility in unexposed portions, and lithography are poor.
< example 100 >
The photosensitive resin composition of example 1 was passed through a filter having a pore width of 0.8 μm, and pressure-filtered, and then the photosensitive resin composition was applied to a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ℃ for 5 minutes to form a photosensitive resin composition layer having a uniform thickness of 15 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was subjected to exposure at 500mJ/cm using a stepper (NiKon NSR 2005i9C)2The exposed photosensitive resin composition layer (resin layer) was developed with cyclopentanone for 60 seconds to form a hole (patterning) having a diameter of 10 μm. Subsequently, the temperature was increased at a rate of 10 ℃/min under a nitrogen atmosphere to 250 ℃, and then the mixture was held at that temperature for 3 hours. After cooling to room temperature, a copper thin layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion. Furthermore, the metal layer and the feelingThe same type of photosensitive resin composition was used again for the surface of the optical resin composition layer, and the sequence from filtration of the photosensitive resin composition to heating of the patterned film for 3 hours was repeated in the same manner as described above to produce a laminate composed of a resin layer/a metal layer/a resin layer.
The resin layer (interlayer insulating film for rewiring layer) has excellent insulating properties.
Then, as a result of manufacturing a semiconductor device using the rewiring layer interlayer insulating film, it was confirmed that the operation was normal.

Claims (23)

1. A photosensitive resin composition comprising:
at least one thermal alkali generator selected from the group consisting of a thermal alkali generator represented by the following formula (B1) and a thermal alkali generator represented by the following formula (B2);
at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors; and
a light-sensitive agent,
the total content of acid groups and acid generating groups contained in the polymer precursor and the sensitizer is 0.5mmol/g or less;
Figure FDA0002704034770000011
in the formulae (B1) and (B2), R1、R2And R3Each independently is an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom, wherein R is1And R2Not simultaneously being a hydrogen atom, and R1、R2And R3Has no carboxyl group.
2. The photosensitive resin composition according to claim 1,
the alkali generation temperature of the thermal alkali generator is 120 ℃ to 200 ℃.
3. The photosensitive resin composition according to claim 1 or 2,
the thermal base generator has a pKa greater than 7.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein,
the polymer precursor comprises a polyimide precursor.
5. The photosensitive resin composition according to claim 4,
the polyimide precursor is represented by the following formula (1),
Figure FDA0002704034770000012
in the formula (1), A1And A2Each independently represents an oxygen atom or NH, R111Represents a 2-valent organic group, R115Represents a 4-valent organic group, R113And R114Each independently represents a hydrogen atom or a 1-valent organic group.
6. The photosensitive resin composition according to any one of claims 1 to 5,
the thermal alkali generator has a molar absorption coefficient of 100l/(mol cm) or less at a wavelength of 365 nm.
7. The photosensitive resin composition according to any one of claims 1 to 6,
the thermal alkali generator contains a thermal alkali generator that generates a base having a conjugate acid pKa of 10 or more by heating.
8. The photosensitive resin composition according to any one of claims 1 to 7, wherein,
the photosensitizer contains a photopolymerization initiator.
9. The photosensitive resin composition according to any one of claims 1 to 8, which is used for development using a developer containing 90% by mass or more of an organic solvent.
10. The photosensitive resin composition according to any one of claims 1 to 9, which is used for formation of an interlayer insulating film for a rewiring layer.
11. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10.
12. The cured film according to claim 11, having a film thickness of 1 to 30 μm.
13. A laminate having 2 or more layers of the cured film of claim 11 or 12.
14. A laminate having 3 to 7 or more layers of the cured film according to claim 11 or 12.
15. The laminate according to claim 13 or 14,
a metal layer is provided between the cured films.
16. A method of manufacturing a cured film, comprising:
a film formation step of applying the photosensitive resin composition according to any one of claims 1 to 10 to a substrate to form a film.
17. The method for producing a cured film according to claim 16, which comprises an exposure step of exposing the film to light and a development step of developing the film.
18. The method for producing a cured film according to claim 17, wherein,
the developer used for the development contains 90 mass% or more of an organic solvent.
19. The method for manufacturing a cured film according to any one of claims 16 to 18, comprising:
heating the film at 80 to 450 ℃.
20. A method for manufacturing a laminate, which is performed a plurality of times by the method for manufacturing a cured film according to any one of claims 16 to 19.
21. A semiconductor device having the cured film of claim 11 or 12 or the laminate of any one of claims 13 to 15.
22. A thermoalcaligenic agent represented by the following formula (B1) or formula (B2),
Figure FDA0002704034770000031
in the formulae (B1), (B2), R1、R2And R3Each independently is an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom, wherein R is1And R2Not simultaneously being a hydrogen atom, and R1、R2And R3Has no carboxyl group.
23. The thermal alkali generator according to claim 22, which is a photosensitive resin composition developed using a developer containing 90% by mass or more of an organic solvent.
CN201980022753.3A 2018-03-29 2019-03-26 Photosensitive resin composition, cured film, laminate, method for producing same, semiconductor device, and thermal alkali generator used for same Pending CN111919172A (en)

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