CN116802560A - Photosensitive resin composition, method for producing polyimide cured film using same, and polyimide cured film - Google Patents

Photosensitive resin composition, method for producing polyimide cured film using same, and polyimide cured film Download PDF

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Publication number
CN116802560A
CN116802560A CN202280011177.4A CN202280011177A CN116802560A CN 116802560 A CN116802560 A CN 116802560A CN 202280011177 A CN202280011177 A CN 202280011177A CN 116802560 A CN116802560 A CN 116802560A
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photosensitive resin
resin composition
polyimide
group
mass
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松本凉香
渋井智史
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Asahi Kasei Corp
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Asahi Kasei 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
    • 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
    • C08G73/12—Unsaturated polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Abstract

A photosensitive resin composition or the like having low dielectric characteristics and low moisture permeability and capable of forming a cured relief pattern with high resolution is provided. The photosensitive resin composition of the present disclosure includes 100 parts by mass of at least one resin selected from polyimide and polyimide precursor, 0.5 to 10 parts by mass of a sensitizer, and 100 to 300 parts by mass of a solvent. The polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃ has an imide group concentration of 12 to 26wt%, and the resin contains a structure represented by the following general formula (14).

Description

Photosensitive resin composition, method for producing polyimide cured film using same, and polyimide cured film
Technical Field
The present disclosure relates to a photosensitive resin composition, a method for producing a polyimide cured film using the same, and a polyimide cured film.
Background
Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which have excellent heat resistance, electrical characteristics, and mechanical characteristics, have been used as insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films, and the like. Among these resins, a photosensitive resin composition can be easily formed into a heat-resistant relief pattern coating by a provider of the composition, such as application, exposure, development, and a closed-loop treatment (imidization, benzoxazolization) by curing, and thermal crosslinking. Such a photosensitive resin composition has a feature that the process can be greatly shortened as compared with conventional non-photosensitive materials, and is used for manufacturing semiconductor devices.
In addition, a semiconductor device (hereinafter, also referred to as an "element") is mounted on a printed board by various methods according to purposes. Conventional devices are generally manufactured by a wire bonding method in which an external terminal (pad) of the device is connected to a lead frame with a thin wire. However, in recent years, the speed of the device has increased and the operating frequency has reached GHz, and the difference in wiring length between terminals at the time of mounting has affected the operation of the device. Therefore, in the mounting of components for high-end use, it is necessary to accurately control the length of the mounting wiring, and it has been difficult to satisfy the requirement for wire bonding.
Accordingly, flip chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, and after bumps (electrodes) are formed thereon, the chip is flipped over (flipped over) and directly mounted on a printed substrate. Since the flip chip mounting can accurately control the wiring distance, the flip chip mounting is used for a device for high-end use for processing a high-speed signal, or for a mobile phone or the like because of its small mounting size, and the demand is rapidly expanding. In addition, a semiconductor chip mounting technology called fan-out wafer level package (FOWLP) has recently been proposed in which a wafer after completion of a preceding step is diced to manufacture individual chips, the individual chips are reconstituted on a support and sealed with a molding resin, and a rewiring layer is formed after the support is peeled off (for example, patent document 1). The fan-out wafer level package has the following advantages: since the rewiring layer can be formed with a small film thickness, the package can be made thin, and high-speed transportation and low-cost can be achieved.
In recent years, with a remarkable increase in information traffic, it has been necessary to speed up communications at a level higher than the prior art, and it has been necessary to shift to communications in the 5 th generation communications (5G) using frequencies higher than 3GHz or in the ultra-high frequency band from the quasi-millimeter wave band (20 GHz to 30 GHz) to the millimeter wave band (30 GHz or more) in which a wider frequency bandwidth is easily secured, and it has been necessary to cope with high frequencies not only for printed boards but also for semiconductor chips mounted on boards. Therefore, in order to reduce transmission loss, a package Antenna (AiP) has been developed in which a Front End Module (FEM) for transmitting and receiving radio waves and an antenna are integrated (for example, refer to patent document 2 below). AiP can suppress transmission loss which increases in proportion to the wiring length because of the short wiring length.
In general, transmission loss increases as the frequency of an electrical signal becomes higher. It is generally considered that there are two methods for reducing transmission loss in a high frequency band, namely, a method for reducing dielectric loss and a method for reducing conductor loss. The former requires a photosensitive resin composition having low dielectric characteristics (low dielectric loss tangent and low dielectric constant) (for example, patent document 3). In the latter case, it is desirable to reduce the roughness of the metal rewiring layer.
As an interlayer material for protecting the rewiring layer, not only low dielectric characteristics but also high adhesion between the rewiring metal layer and the resin layer is required from the viewpoint of reliability, and particularly in recent years, a lower temperature for heat curing of the rewiring layer is required. Patent document 4, for example, discloses such a photosensitive resin composition.
Prior art literature
Patent literature
Patent document 1 Japanese patent laid-open publication No. 2005-167191
Patent document 2 U.S. patent application publication 2016/0104940
Patent document 3 International publication No. 2019/044874
Patent document 4 Japanese patent application laid-open No. 2018-200470
Disclosure of Invention
Problems to be solved by the invention
In recent years, due to the diversification of package mounting technologies, the variety of supports has become diversified, and the rewiring layers have also become multilayered, so that the influence of the dielectric constant and dielectric loss tangent (tan δ) of an insulating material used for forming wirings has become large. When the dielectric constant and the dielectric loss tangent are high, the dielectric loss increases, resulting in an increase in transmission loss. Polyimide resins are considered to have high dielectric constant and dielectric loss tangent due to the effects of polar functional groups derived from imide groups, the addition of polar functional groups for photosensitivity, additives, and the like, while having high material reliability due to excellent insulating properties and thermo-mechanical properties. In addition, the frequency dependence of the dielectric loss tangent may be a problem, and it is considered that the moisture permeability of the insulating layer is preferably low.
An object of the present disclosure is to provide a photosensitive resin composition having low dielectric characteristics and low moisture permeability, capable of forming a cured relief pattern with high resolution; and a method for producing a polyimide cured film using the same, and a polyimide cured film.
Solution for solving the problem
Examples of embodiments of the present disclosure are listed in items [1] to [19] below.
[1] A photosensitive resin composition comprising:
(A) 100 parts by mass of at least one resin selected from polyimide and polyimide precursor;
(B) 0.5 to 10 parts by mass of a sensitizer; and
(C) 100-300 parts by mass of a solvent;
in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃, the concentration U of imide groups is 12-26 wt%, the concentration U of imide groups is the proportion of the molecular weight of imide groups relative to the molecular weight of repeating units containing a structure derived from tetracarboxylic dianhydride and diamine,
the resin contains a structure represented by the following general formula (14).
{ in which R 15 Is an organic group with 1-5 carbon atoms, R 16 、R 17 R is R 18 Each independently is a single bond optionally forming a ring structure or an alkyl group having 1 to 10 carbon atoms optionally forming a ring structure or an organic group containing an aromatic ring having 6 to 10 carbon atoms, m 9 Is an integer selected from 1 to 4, m 10 、m 11 M 12 Each independently is an integer selected from 0 to 4, Z 2 The term "organic group having a single bond or a hetero atom" or an organic group having 1 to 13 carbon atoms "means a linking portion with the main chain of the resin. }
[2] The photosensitive resin composition according to item 1, wherein the aliphatic hydrocarbon group concentration T is 4 to 35wt% in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃, and the aliphatic hydrocarbon group concentration T is a ratio of the total of the molecular weights of the aliphatic hydrocarbon groups to the molecular weight of the repeating unit including the structure derived from the tetracarboxylic dianhydride and the diamine compound.
[3] The photosensitive resin composition according to item 1 or 2, wherein the structure represented by the general formula (14) is derived from a diamine.
[4] The photosensitive resin composition according to any one of items 1 to 3, wherein the resin is a polyimide precursor.
[5] The photosensitive resin composition according to item 4, wherein the polyimide precursor comprises a structure represented by the following general formula (4).
{ in X 1 Is a C6-40 organic group of 4 valence, Y 1 An organic group having a valence of 2 and having 6 to 40, n 1 R is an integer of 2 to 150 4 And R is 5 Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 40 carbon atoms. Wherein R is 4 And R is 5 At least one of them is a group represented by the following general formula (5). }
{ in which R 6 、R 7 And R is 8 Each independently is a hydrogen atom or a 1-valent organic group having 1 to 3 carbon atoms, and m 2 Is an integer of 2 to 10. }
[6] A photosensitive resin composition comprising:
(A) 100 parts by mass of at least one resin selected from polyimide and polyimide precursor;
(B) 0.5 to 10 parts by mass of a sensitizer; and
(C) 100-300 parts by mass of a solvent;
when the resin contains a polyimide precursor, the polyimide precursor is represented by the following general formula (4),
{ in X 1 Is a C6-40 organic group of 4 valence, Y 1 An organic group having a valence of 2 and having 6 to 40, n 1 R is an integer of 2 to 150 4 And R is 5 Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 40 carbon atoms. Wherein R is 4 And R is 5 At least one of them is a group represented by the following general formula (5). }
{ in which R 6 、R 7 And R is 8 Each independently is a hydrogen atom or a 1-valent organic group having 1 to 3 carbon atoms, and m 2 Is an integer of 2 to 10. }
The resin contains a structure represented by the following general formula (15),
{ wherein Rz each independently represents a 1-valent organic group having 1 to 10 carbon atoms optionally containing a halogen atom and optionally forming a cyclic structure, a represents an integer of 0 to 4, A is each independently an oxygen atom or a sulfur atom, and B is 1 of the following formulas:
The resin contains a structure represented by the following general formula (14),
{ in which R 15 Is an organic group with 1-5 carbon atoms, R 16 、R 17 R is R 18 Each independently is a single bond optionally forming a ring structure or an alkyl group having 1 to 10 carbon atoms optionally forming a ring structure or an organic group containing an aromatic ring having 6 to 10 carbon atoms, m 9 Is an integer selected from 1 to 4, m 10 、m 11 M 12 Each independently is an integer selected from 0 to 4, Z 2 The term "organic group having a single bond or a hetero atom" or an organic group having 1 to 13 carbon atoms "means a linking portion with the main chain of the resin. }.
[7] A photosensitive resin composition comprising:
(A) 100 parts by mass of at least one resin selected from polyimide and polyimide precursor;
(B) 0.5 to 10 parts by mass of a sensitizer; and
(C) 100-300 parts by mass of a solvent;
in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃, the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit including the structure derived from the tetracarboxylic dianhydride and the diamine is set to be the imide group concentration U, and the ratio of the total molecular weight of the aliphatic hydrocarbon groups to be the aliphatic hydrocarbon group concentration T is set to be 12 to 26wt%, and the following formula (1) is satisfied:
-12.6＜U-T＜16.0 (1)。
[8] A photosensitive resin composition comprising:
(A) 100 parts by mass of at least one resin selected from polyimide and polyimide precursor;
(B) 0.5 to 10 parts by mass of a sensitizer; and
(C) 100-300 parts by mass of a solvent;
in the IR spectrum of a polyimide obtained by heating and curing the polyimide precursor (A) at 230 ℃, the polyimide precursor (A) was brought to 1450cm -1 1550cm above -1 The maximum peak intensity among the absorption peaks in the following range was set to Ph 1 Setting the second highest peak intensity to Ph 2 Will 1380cm -1 The peak intensity in the vicinity is set to Im 1 And set Ph 1 When normalized for 1, the following formula (2) is satisfied:
0.34≤Ph 2 ×Im 1 ≤1.2 (2)。
[9] the photosensitive resin composition according to any one of items 1 to 8, wherein the resin is a reaction product of tetracarboxylic dianhydride and diamine.
[10] The photosensitive resin composition according to item 9, wherein at least one of the tetracarboxylic dianhydrides and at least one of the diamines constituting the resin have an aliphatic hydrocarbon group.
[11] The photosensitive resin composition according to any one of items 1 to 10, further comprising (D) a silane coupling agent.
[12] The photosensitive resin composition according to any one of items 1 to 11, further comprising (E) a radical polymerizable compound.
[13] The photosensitive resin composition according to item 12, wherein the radical polymerizable compound (E) has an alkyl group.
[14] The photosensitive resin composition according to any one of items 1 to 13, further comprising (F) a thermal crosslinking agent.
[15] The photosensitive resin composition according to any one of items 1 to 14, further comprising (G) a filler.
[16] A method for producing a polyimide cured film, comprising the steps of:
a step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of items 1 to 15 to the substrate;
a step of heating and drying the photosensitive resin layer obtained;
exposing the heated and dried photosensitive resin layer to light;
developing the photosensitive resin layer after exposure; and
and a step of forming a polyimide cured film by heat-treating the developed photosensitive resin layer.
[17] The method of producing a cured polyimide film according to item 16, wherein the coating to developing steps are performed so as to obtain a photosensitive resin layer having a thickness of 10 μm to 15 μm in the developing step, and a developing time during development is 30 seconds or less.
[18] A polyimide cured film having a dielectric loss tangent of 0.003 to 0.014 at a frequency of 40GHz by a perturbed split cylindrical resonator method and satisfying the following formula (3):
3＜tanδ 40 ×WVTR＜10 (3)
{ in tan delta 40 The representation is based on perturbed splittingThe dielectric loss tangent at 40GHz of the frequency of the cylindrical resonator method, WVTR, represents the moisture permeability of the cured polyimide film converted to a film thickness of 10. Mu.m. }.
[19] The photosensitive resin composition according to any one of items 1 to 15, wherein the photosensitive resin composition is used for a rewiring layer.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the photosensitive resin composition of the present disclosure, a cured resin film having excellent resolution of a relief pattern, low dielectric characteristics, low moisture permeability, and good chemical resistance can be produced. By using a polyimide precursor having a specific terminal crosslinking group and aliphatic hydrocarbon group, the solubility of the pre-baked film in a developer is improved, and thus the resolution of the relief pattern is improved. In addition, the hydrophobicity and the crosslink density of the cured film are increased, whereby the moisture permeability is lowered, the chemical resistance is improved, and the repulsive volume is increased, whereby the dielectric loss tangent is lowered.
Drawings
FIG. 1 shows an example of IR spectrum of a polyimide obtained by heat-curing a polyimide precursor at 230 ℃.
Detailed Description
Embodiments of the present disclosure are described in detail below. In the present specification, when a plurality of structures represented by the same symbols in the general formula are present in a molecule, the structures may be the same or different from each other, and are independently selected unless otherwise specified. The structures represented by the same symbols in different formulae may be the same or different from each other, and are selected independently unless otherwise specified.
Photosensitive resin composition
The photosensitive resin composition of the present disclosure contains: 100 parts by mass of at least one resin selected from the group consisting of polyimide and polyimide precursor having a specific structure, (B) 0.5 to 10 parts by mass of a photopolymerization initiator, and (C) 50 to 500 parts by mass of a solvent. The photosensitive resin composition of the present disclosure further contains (D) a silane coupling agent, (E) a compound containing an ethylenically unsaturated group, (F) a thermal crosslinking agent, (G) a filler, and other components, as desired, in addition to the above components.
[ (A) polyimide and polyimide precursor ]
From the viewpoints of resolution, moisture permeability and low dielectric loss tangent, the resin (a) is preferably at least one resin selected from the group consisting of polyimide and polyimide precursor, and has a structure represented by the following general formula (14).
{ in which R 15 Is an organic group with 1-5 carbon atoms, R 16 、R 17 R is R 18 Each independently is a single bond optionally forming a ring structure or an alkyl group having 1 to 10 carbon atoms optionally forming a ring structure or an organic group containing an aromatic ring having 6 to 10 carbon atoms, m 9 Is an integer selected from 1 to 4, m 10 、m 11 M 12 Each independently is an integer selected from 0 to 4, Z 2 The term "organic group having a single bond or a hetero atom" or an organic group having 1 to 13 carbon atoms "means a linking portion with the main chain of the resin. }
In the above general formula (14), Z 2 The structure is preferably selected from a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and the organic group having a heteroatom is preferably selected from the structures of the following formulas. An organic group having a heteroatom refers to an organic group having at least 1 heteroatom selected from N, O, P, S, cl, I, br. The organic group may be an unsaturated hydrocarbon or a saturated hydrocarbon, and is more preferably a saturated hydrocarbon. The organic group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
By the structure comprising the above general formula (14), a cured film having a good resolution of the relief pattern and low moisture permeability can be obtained. While not being bound by theory, it is believed that the solubility of the polyimide precursor in the developer is improved by introducing an organic group into the aromatic ring, and the contrast with the exposed portion is easily ensured, thereby improving the resolution of the relief pattern. In addition, although not being bound by theory, the hydrophobicity of the film becomes high and the film becomes less permeable to moisture by introducing an organic group to the aromatic ring.
Examples of the structure of the above general formula (14) include at least one structure selected from the group consisting of the following general formula (9).
When the structure of the formula (14) is derived from tetracarboxylic dianhydride in the preparation of polyimide and a polyimide precursor, it is preferable to include at least one structure selected from the group consisting of the following general formula (10).
When the structure of the formula (14) is derived from a diamine compound used for producing a polyimide or a polyimide precursor, it is preferable to include at least one structure selected from the group consisting of the following general formula (11).
The structure of the general formula (14) is not limited to the structures listed in the above (9) to (11). The number of the above-mentioned structures may be 1 or a combination of 2 or more.
From the viewpoints of resolution, moisture permeability and low dielectric loss tangent, the resin (a) is preferably composed of a structure represented by the following general formula (15) and at least one resin selected from polyimide and a polyimide precursor.
{ wherein Rz each independently represents a 1-valent organic group having 1 to 10 carbon atoms optionally containing a halogen atom and optionally forming a cyclic structure, a represents an integer of 0 to 4, A is each independently an oxygen atom or a sulfur atom, and B is a single bond or 1 of the following formulas:
in the photosensitive resin composition of the present disclosure, the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition has an imide group concentration U of 12 to 26wt%. In the present specification, "imide group concentration U" means: in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃, the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit including the structure derived from the tetracarboxylic dianhydride and the diamine compound is occupied. The condition of heating and curing at 350℃is to specify the aliphatic hydrocarbon group concentration T based on the imidized state of the polyimide precursor of almost 100%, and it is not intended to heat and cure the photosensitive resin composition at 350℃in practical use.
When the imide group concentration U is 12.0wt% or more, the resolution of the relief pattern tends to be good. The imide group concentration U is preferably 12.5wt% or more, more preferably 13.5wt% or more. On the other hand, when the imide group concentration U is 26wt% or less, the dielectric loss tangent of the obtained polyimide cured film tends to be good. The imide group concentration U is more preferably 23.0wt% or less, and still more preferably 21.0wt% or less.
The imide group concentration U in the repeating unit of the polyimide cured film can be represented by the following formula (I) using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in the preparation of the polyimide precursor.
70.02×2/[Mw(A)+Mw(B)-36]×100(I)
In the { formula (I), mw (A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw (B) represents the molecular weight of the diamine. }. In the case of using 2 or more kinds of tetracarboxylic dianhydride and/or diamine compounds, for example, in the case of using 2 kinds of tetracarboxylic dianhydride and/or diamine compounds, the compound is represented by the following formula (II).
70.02×2/[Mw(A1)×a 1 +Mw(A2)×a 2 +Mw(B1)×b 1 +Mw(B2)×b 2 -36]×100(II)
{ in formula (II), mw (A1) represents the molecular weight of the first tetracarboxylic dianhydride, mw (A2) represents the molecular weight of the second tetracarboxylic dianhydride, a 1 Represents the content of the first tetracarboxylic dianhydride, a 2 Represents the content of the second tetracarboxylic dianhydride, mw (B1) represents the molecular weight of the first diamine compound, mw (B2) represents the molecular weight of the second diamine compound, B 1 Represents the content of the first diamine compound, and b 2 Represents the content of the second diamine compound. Wherein a is 1 、a 2 、b 1 、b 2 Respectively satisfy a 1 +a 2 ＝1、b 1 +b 2 =1. }. The same applies when 3 or more tetracarboxylic dianhydrides and/or diamines are used. When tetracarboxylic acid and/or tetracarboxylic acid dichloride are used as the raw material, the mass of the corresponding tetracarboxylic dianhydride is used for calculation.
The polyimide and/or polyimide precursor resin optionally has at least one terminal structure selected from the group consisting of the following general formulae (1) to (3).
{ in the formula, W is an organic group having a valence of 2 to 3, R 1 ～R 3 Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 3 carbon atoms, m 1 Is an integer of 1 to 2, m 2 Is an integer of 2 to 10, and represents a bond with the main chain of the resin. }. By providing polyimide and/or polyimide precursor with such a terminal structure, a negative photosensitive resin composition having low dielectric characteristics, low moisture permeability, good chemical resistance, and high resolution can be obtained.
The structure of W is not particularly limited, but is preferably an organic group having a weight average molecular weight of less than 300 and having a valence of 2 to 3, more preferably an organic group having a valence of 2 to 3 having a carbon number of 1 to 5, and still more preferably an organic group having a valence of 2 to 3 having a carbon number of 1 to 3.
(A) The polyimide precursor optionally has a polymerizable group at the end of the main chain. The polyimide precursor (a) having a polymerizable group preferably has a structure represented by the following general formula.
{ formula (E1), a 1 Comprising at least 1 bond of amide bonds, imide bonds, urea bonds, urethane bonds, b 1 E is a reactive substituent which is crosslinked by heat or light 1 Is a 1-valent organic group with 1-30 carbon atoms, R 19 、R 22 R is independently a hydrogen atom or a 1-valent organic group having 1 to 30 carbon atoms 20 、R 21 Each independently represents any one of a hydrogen atom, a 1-valent organic group having 1 to 30 carbon atoms, an aromatic ring, and a part of an aliphatic ring. Wherein R is 20 And R is 21 Not both hydrogen atoms. }
(wherein f 1 Comprises at least 1 bond of amide bond, imide bond, urea bond, urethane bond, and ester bond, g 1 R is a reactive substituent which is crosslinked by heat or light 23 ～R 27 Each independently represents a hydrogen atom, a 1-valent organic group having 1 to 30 carbon atoms, or an aromatic ring or an aliphatic ring. Wherein R is 24 、R 25 、R 26 Not both hydrogen atoms. ). By providing the polyimide precursor with a polymerizable group at such a terminal, a negative photosensitive resin composition having low dielectric characteristics, low moisture permeability, good chemical resistance, and high resolution can be obtained.
f 1 Preferably at least 1 group of an amide group, an imide bond, an urea group and a urethane group. f (f) 1 In the case of an ester group, the ester group is easily hydrolyzed, and thus there is a possibility that crosslinking is not performed. These 4 groups (amide groupImide bond, ureido group, and urethane group) is not easily hydrolyzed, and thus has high chemical resistance.
Reactive substituents b crosslinked by heat or light 1 For example, at least one selected from the group consisting of an acryl group, a methacryl group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cyclodienyl group, a styryl group, an ethynyl group, an imino group, an isocyanate group, a cyanate group, a cycloalkyl group, an epoxy group, an oxetanyl group, a carbonate group, a hydroxyl group, a mercapto group, a hydroxymethyl group, and an alkoxyalkyl group is preferable. B from the viewpoint of film thickness uniformity 1 Preferably at least one selected from the group consisting of acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cyclodienyl, styryl, and ethynyl. Methacryloyl group is particularly preferred.
Reactive substituents g crosslinked by heat or light 1 For example, at least one member selected from the group consisting of an acryl group, a methacryl group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkenyl group, a dienyl group, a cyclodienyl group, a styryl group, an ethynyl group, an imino group, an isocyanate group, a cyanate group, a cycloalkyl group, an epoxy group, an oxetanyl group, a carbonate group, a hydroxyl group, a mercapto group, a hydroxymethyl group, and an alkoxyalkyl group. From the viewpoint of film thickness uniformity, g 1 Preferably at least one selected from the group consisting of acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cyclodienyl, styryl, and ethynyl. g 1 Methacryloyl group is particularly preferred.
Specific examples of the compound having a reactive substituent which reacts with heat or light and also having a site which reacts with a carboxyl group and the main chain terminal of the polyimide precursor modified with the reactive substituent are shown below.
The aliphatic hydrocarbon group concentration T of the polyimide cured film obtained by heating and curing the photosensitive resin composition is preferably 4 to 35wt%. In the present specification, "aliphatic hydrocarbon group concentration T" means: in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃, the total of the molecular weights of the aliphatic hydrocarbon groups is a proportion of the molecular weight of the repeating unit formed from the tetracarboxylic dianhydride and the diamine compound. The reason why the heating and curing at 350℃are used as the reference is that the aliphatic hydrocarbon group concentration T is easily adjusted based on the state of imidization of almost 100% of the polyimide precursor, and it is not intended to heat and cure the photosensitive resin composition at 350℃in practical use. The term "aliphatic hydrocarbon group" as used herein refers to a hydrocarbon group having at least one structure selected from the group consisting of a saturated aliphatic chain, an unsaturated aliphatic chain and an alicyclic structure, branched from a polyimide precursor main chain, and may be any of a straight chain and a branched chain. The alkylene skeleton portion constituting a part of the main chain, the quaternary carbon constituting a part of the main chain (carbon which is disubstituted and constitutes a part of the main chain) is not contained in the "aliphatic hydrocarbon group" in calculating the concentration of the aliphatic hydrocarbon group. The aliphatic hydrocarbon group constituting the side chain portion branched from the main chain is contained in the "aliphatic hydrocarbon group" in the calculation of the concentration of the aliphatic hydrocarbon group, regardless of whether it is saturated or unsaturated or chain-like or alicyclic. Examples of the structure of the "aliphatic hydrocarbon group" include structures represented by the following general formula (A1), the following general formula (A2) and the following general formula (A3).
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In the general formulae (A1) to (A3), L is a single bond or an organic group having a valence which is optionally any one of a linear or branched saturated hydrocarbon and a linear or branched unsaturated hydrocarbon, b is an integer of 1 to 6, R a1 Is an organic group having 1 to 8 carbon atoms or a hydrogen atom optionally having a ring structure. And is a linking group with a backbone structure.
From the viewpoint of the dielectric loss tangent of the polyimide cured film, the aliphatic hydrocarbon group preferably has a monovalent aliphatic saturated hydrocarbon group having 1 to 3 carbon atoms, for example, a methyl group. When the group concentration T is 4wt% or more, the dielectric loss tangent of the polyimide cured film tends to be good. The aliphatic hydrocarbon group concentration T is preferably 5wt% or more, more preferably 7wt% or more, and still more preferably 8wt% or more. When the aliphatic hydrocarbon group concentration T is 5wt% or more, the moisture permeability tends to be good. On the other hand, when the aliphatic hydrocarbon group concentration T is 35wt% or less, the polyimide cured film obtained tends to have good resolution and moisture permeability. The aliphatic hydrocarbon group concentration T is more preferably 28wt% or less, still more preferably 17wt% or less, and still more preferably 12 wt% or less.
The aliphatic hydrocarbon group concentration T can be represented by the following formula (I) using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in the preparation of the polyamide and/or polyimide precursor.
[Mw(P)+Mw(Q)]/[Mw(A)+Mw(B)-36]×100(I)
{ in formula (I), mw (P) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the tetracarboxylic dianhydride, mw (Q) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the diamine compound, mw (A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw (B) represents the molecular weight of the diamine compound. }
When 2 or more tetracarboxylic dianhydrides and/or diamine compounds are used, for example, when 2 tetracarboxylic dianhydrides and 2 diamine compounds are used, the composition is represented by the following formula (II).
[Mw(P1)×a 1 +Mw(P2)×a 2 +Mw(Q1)×b 1 +Mw(Q2)×b 2 ]/[Mw(A1)×a 1 +Mw(A2)×a 2 +Mw(B1)×b 1 +Mw(B2)×b 2 -36]×100(II)
{ formula (II), mw (P1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first tetracarboxylic dianhydride, mw (P2) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the second tetracarboxylic dianhydride, mw (Q1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first diamine compound, and Mw (Q2) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the second diamine compound. Mw (A1) represents the molecular weight of the first tetracarboxylic dianhydride, mw (A2) represents the molecular weight of the second tetracarboxylic dianhydride, a 1 Represents the content ratio of the first tetracarboxylic dianhydride, a 2 Represents a second tetracarboxylic acid dicarboxylic acidAnhydride content ratio. Mw (B1) represents the molecular weight of the first diamine compound, mw (B2) represents the molecular weight of the second diamine compound, B 1 Represents the content ratio of the first diamine compound, and b 2 The content ratio of the second diamine compound is shown. In addition, a 1 、a 2 、b 1 、b 2 Respectively satisfy a 1 +a 2 ＝1、b 1 +b 2 =1. The same applies to the case where 3 or more tetracarboxylic dianhydride and/or diamine compounds are used. When tetracarboxylic acid and/or tetracarboxylic acid chloride are used as the raw material, the molecular weight of the corresponding tetracarboxylic dianhydride is used for calculation.
At least one of the tetracarboxylic dianhydride and the diamine compound preferably has an aliphatic hydrocarbon group. When the diamine compound has an aliphatic hydrocarbon group, the moisture permeability tends to be low, and thus it is preferable. When both the diamine compound and the tetracarboxylic dianhydride have aliphatic hydrocarbon groups, the solubility in a developer tends to be improved, and the development speed tends to be improved, and therefore, it is preferable.
In the IR spectrum of a polyimide obtained by heating and curing the polyimide precursor (A) at 230 ℃, the polyimide precursor (A) was brought to 1450cm -1 1550cm above -1 The maximum peak intensity among the absorption peaks in the following range was set to Ph 1 Setting the second highest peak intensity to Ph 2 Will 1380cm -1 The peak intensity in the vicinity is set to Im 1 And set Ph 1 When normalized for 1, the following formula (2) is preferably satisfied:
0.34≤Ph 2 ×Im 1 ≤1.2 (2)。
the measurement conditions of the IR spectrum were carried out by the method described in examples described below. The peak intensity at the low wavelength side and the peak intensity at the high wavelength side of the peak top are each a value lower than the peak intensity at the peak top, and are not regarded as peaks when either the peak intensity at the low wavelength side or the peak intensity at the high wavelength side is a value higher than the peak intensity at the peak top.
For example, in the case of polyimide having an IR spectrum shown in the graph of fig. 1, ph 1 ＝1(1500cm -1 )，Ph 2 ＝0.42(1473cm -1 )，Im 1 ＝0.68(1373cm -1 ). At Ph 1 High frequency side (1512 cm) -1 ) The observed signal is not considered as a peak.
At 1450cm -1 1550cm above -1 When there is only one peak in the following range, ph 2 Set to 0. 1380cm -1 The peak intensity in the vicinity is + -10 cm from each wave number -1 The largest peak in the range of (2) is taken as peak intensity.
By making Ph 2 ×Im 1 Preferably 0.34 or more, more preferably 0.36 or more, more preferably 0.40 or more, and 0.45 or more, and the resolution tends to be good. While not being bound by theory, it is believed that by letting Ph 2 ×Im 1 When the solubility of the polyimide precursor is 0.34 or more, the resolution is improved. On the other hand, by making Ph 2 ×Im 1 Preferably 1.2 or less and 1.1 or less, the dielectric loss tangent tends to be good. While not being bound by theory, it is believed that by letting Ph 2 ×Im 1 The molecular motion in the high frequency region is reduced to 1.2 or less.
The polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃ preferably satisfies the following formula (1).
-12.6＜U-T＜16.0 (1)
In the formula { formula, U represents the imide group concentration of polyimide, and T represents the aliphatic hydrocarbon group concentration of polyimide. }. The U-T is preferably-12.6 or more, more preferably-11.0 or more, and-10 or more, and the resolution tends to be excellent. The U-T is preferably 16.0 or less, more preferably 12.5 or less, still more preferably 12.0 or less, and preferably 11.0 or less, whereby the moisture permeability tends to be excellent. The reason why the heating and curing at 350 ℃ are used as the reference is to easily adjust the aliphatic hydrocarbon group concentration T based on the state that the polyimide precursor is almost 100% imidized, and it is not intended to heat and cure the photosensitive resin composition at 350 ℃ in practical use.
The polyimide precursor (a) may be a polyamide precursor having a structural unit represented by the following general formula (4).
{ in X 1 Is a C6-40 organic group of 4 valence, Y 1 An organic group having a valence of 2 and having 6 to 40, n 1 R is an integer of 2 to 150 4 And R is 5 Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 40 carbon atoms. Wherein R is 4 And R is 5 At least one of them is a group represented by the following general formula (5). }
{ in which R 6 、R 7 And R is 8 Each independently is a hydrogen atom or a 1-valent organic group having 1 to 3 carbon atoms, and m 2 Is an integer of 2 to 10. }. R in the general formula (4) 4 R is R 5 Also known as side chains or side chain structures of polyimide precursors. R in the above general formula (5) 6 Preferably hydrogen or methyl, R 7 R is R 8 From the viewpoint of photosensitivity, a hydrogen atom is preferable. In addition, m 2 From the viewpoint of photosensitivity, the integer is 2 to 10, preferably 2 to 4.
From the viewpoints of resolution and low dielectric characteristics, the proportion of photosensitive groups per repeating unit in the polyimide precursor resin (a) represented by the general formula (4) is preferably 15 to 35wt%. From the viewpoint of dielectric characteristics, it is preferable that the photosensitive groups are small, and from the viewpoint of resolution, it is preferable that the photosensitive groups are large. In the present specification, "proportion of photosensitive groups" means: the proportion of the molecular weight of the photopolymerizable group-containing compound constituting the repeating unit based on the molecular weight of the entire repeating unit represented by the above general formula (4). Examples of the photopolymerizable group include an unsaturated double bond.
The proportion of the photosensitive group in each repeating unit of the polyimide precursor resin can be represented by the following formula (I) using the molecular weights of the tetracarboxylic dianhydride and the diamine compound used in the preparation of the polyimide precursor.
[Mw(R)]/[Mw(A)+Mw(B)+Mw(R)-36]×100(I)
{ in formula (I), mw (R) represents the sum of the molecular weights of the photopolymerizable group-containing compounds (photopolymerizable group-containing compounds), mw (a) represents the molecular weight of the tetracarboxylic dianhydride, and Mw (B) represents the molecular weight of the diamine compound. }
When 2 or more tetracarboxylic dianhydride and/or diamine compounds are used, the calculation is performed based on the ratio of the raw materials in the same manner as the definition of the aliphatic hydrocarbon group concentration T.
In the case of a copolymer of a photopolymerizable group-containing compound and a photopolymerizable group-free compound, the following formula (II) is used.
[Mw(R)×c 1 ]/[Mw(A)+Mw(B)+Mw(R)×c 1 +Mw(S)×c 2 -36]×100(II)
{ in formula (II), mw (R) represents the sum of the molecular weights of the photopolymerizable group-containing compounds, mw (S) represents the sum of the molecular weights of the photopolymerizable group-free compounds, mw (A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw (B) represents the molecular weight of the diamine compound. c 1 C represents the content of the photopolymerizable group-containing compound 2 Represents the content of the photopolymerizable group-free compound, and c 1 、c 2 Respectively satisfy c 1 +c 2 =1. }. When tetracarboxylic acid and/or tetracarboxylic acid chloride are used as the starting material, the molecular weight of the corresponding tetracarboxylic dianhydride is used for calculation.
From the viewpoints of photosensitive properties and mechanical properties of the photosensitive resin composition, n in the general formula (4) is as follows 1 Preferably an integer of 3 to 100, more preferably an integer of 5 to 70.
In the above general formula (4), X 1 The organic group having 4 valence is preferably an organic group having 6 to 40 carbon atoms, more preferably-COOR, from the viewpoint of heat resistance and photosensitivity 1 Radical and-COOR 2 An aromatic group or an alicyclic group in which the group and the-CONH-group are ortho to each otherAliphatic groups. As X 1 The organic group having a valence of 4 is specifically an organic group having 6 to 40 containing an aromatic ring, for example, a group having a structure represented by the following general formula (7),
{ in formula (7), R 11 Is a 1-valent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group and a C1-C10 fluorine-containing hydrocarbon group, m 5 Is an integer of 0 to 2, m 6 Is an integer of 0 to 3, and m 7 Is an integer of 0 to 4. But are not limited to these. In addition, X 1 The number of the structures may be 1 or a combination of 2 or more. X having the structure represented by the above formula (7) is particularly preferable from the viewpoint of both heat resistance and photosensitivity 1 A base.
In the above general formula (4), Y 1 The organic group having a valence of 2 is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of heat resistance and photosensitivity, and examples thereof include groups having a structure represented by the following general formula (8).
{ in formula (8), R 11 Is a 1-valent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group and a C1-C10 fluorine-containing hydrocarbon group, m 5 Is an integer of 0 to 2, m 6 Is an integer of 0 to 3, and m 7 Is an integer of 0 to 4. But are not limited to these. In addition, Y 1 The number of the structures may be 1 or a combination of 2 or more. From the viewpoint of both heat resistance and photosensitivity, Y having a structure represented by the above formula (8) is particularly preferable 1 A base.
(A) Among polyimide precursors, X as a skeleton component derived from a tetracarboxylic acid compound is preferable 1 Or Y as a backbone component derived from a diamine compound 1 Is to of (a)Any one of them has a structure in which 2 or more benzene rings are bonded. The number of benzene rings may be 3 or more or 4 or more and 6 or less, 5 or less or 4 or less, more preferably 4. By providing the polyimide precursor (a) with such a structure, the resolution of the negative photosensitive resin composition is maintained, and the cured relief pattern obtained tends to have low dielectric characteristics.
In the above general formula (4), Y 1 The organic group of valence 2 shown preferably has the structure of the above general formula (14). By Y in the formula (4) 1 The structure comprising the above general formula (14) tends to be excellent in resolution. While not being bound by theory, it is believed that the electron density of the aromatic ring increases, promoting CT migration, and thus inhibiting film expansion upon development.
[ (A) preparation method of polyimide precursor ]
The ester bond type polyimide precursor having at least one terminal structure selected from the group consisting of the above general formulae (1) to (3) can be obtained by any of the following methods. For example, it can be obtained as follows: the esterified tetracarboxylic dianhydride having a terminal structure is synthesized first, followed by amide polycondensation with a diamine compound, thereby obtaining the polymer.
(introduction method of terminal Structure 1)
To form the terminal structures of the general formula (1) and the general formula (2), a desired tetracarboxylic dianhydride having a 4-valent organic group X is reacted with a compound having an isocyanate group, and then an alcohol having a photopolymerizable group (for example, an unsaturated double bond) is reacted to prepare a partially imidized or partially imidized (derived from the structure of the general formula (2)/esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester/imide). In order to promote the reaction of the tetracarboxylic dianhydride with the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1, 4-diazabicyclo [2.2.2] octane and the like can be used. Optionally, a saturated aliphatic alcohol may be used in combination with the above-mentioned alcohol having a photopolymerizable group.
(method for introducing terminal Structure 2)
In order to form the terminal structure of the above general formula (3), a desired tetracarboxylic dianhydride having an organic group X of 4 valence is reacted with an alcohol having a photopolymerizable group (for example, an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester body), and then the compound having an isocyanate group is reacted to prepare a partially esterified/partially amidated tetracarboxylic acid (hereinafter also referred to as an acid/ester/amide body). In order to promote the reaction of the tetracarboxylic dianhydride with the compound having an isocyanate group, pyridine, triethylamine, dimethylaminopyridine, 1, 4-diazabicyclo [2.2.2] octane and the like can be used. Optionally, a saturated aliphatic alcohol may be used in combination with the above-mentioned alcohol having a photopolymerizable group.
(preparation of acid/ester body)
Organic group X having a valence of 4 and having 6 to 40, which is suitable for preparing ester-bond type polyimide precursor 1 In addition to the tetracarboxylic dianhydrides derived from the above-mentioned structures, for example, pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, diphenyl sulfone-3, 3', 4' -tetracarboxylic dianhydride, diphenylmethane-3, 3',4,4' -tetracarboxylic dianhydride, 2-bis (3, 4-phthalic anhydride) propane, 2-bis (3, 4-phthalic anhydride) -1, 3-hexafluoropropane 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, 4' -bis (3, 4-dicarboxyphenoxy) benzophenone dianhydride, and the like, but is not limited to these. It is needless to say that these may be used alone, or 2 or more kinds may be mixed and used.
Using these organic radicals X containing a valence of 4 and having a carbon number of 6 to 40 1 And forming a terminal structure using the above-described introduction method 1 or introduction method 2. The order of the reactions varies depending on the method of introduction.
Examples of the photopolymerizable group-containing compound suitable for synthesizing the esterified tetracarboxylic acid having the reactive terminal represented by the general formulae (1) to (3) include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2- (2-methacryloyloxyethyl oxy) ethyl isocyanate, 1- (bisacrylyloxymethyl) ethyl isocyanate, and the like. Examples of the alcohols having a photopolymerizable group include 2-acryloxyethanol, 1-acryloxy3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethanol, 1-methacryloxy3-propanol, 2-methacrylamidoethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.
The saturated aliphatic alcohols optionally used together with the photopolymerizable group-containing alcohols are preferably saturated aliphatic alcohols having 1 to 4 carbon atoms. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and the like.
The above tetracarboxylic dianhydride and alcohol are stirred and mixed for 4 to 10 hours at a temperature of 20 to 50 ℃ preferably in the presence of a basic catalyst such as pyridine, and the desired acid/ester can be obtained by the esterification reaction of the acid anhydride.
The reaction solvent is preferably a solvent in which tetracarboxylic dianhydride and alcohol as raw materials and the acid/ester as a product are completely dissolved. More preferably, the polyimide precursor is a solvent which can completely dissolve the acid/ester compound and the diamine as an amide polycondensation product. Examples thereof include N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and the like. Specific examples of these ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate. Examples of the lactones include gamma-butyrolactone. Examples of the ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran. Examples of the halogenated hydrocarbon include methylene chloride, 1, 2-dichloroethane, 1, 4-dichlorobutane, chlorobenzene, and o-dichlorobenzene. Examples of the hydrocarbon include hexane, heptane, benzene, toluene, and xylene. These may be used alone or in combination of 2 or more kinds as required.
(preparation of polyimide precursor)
The acid/ester is preferably mixed with a proper dehydration condensing agent under ice cooling to form a polyanhydride. Then dropwise adding a 2-valent organic group Y containing 6 to 40 carbon atoms 1 The diamine of (2) is separately dissolved or dispersed in a solvent, and both are subjected to amide polycondensation, whereby the objective polyimide precursor can be obtained. May also be combined with the above-mentioned organic group Y having 2 valences 1 The diamines of (2) are used in combination with diaminosiloxanes. Examples of the dehydration-condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole, and N, N' -disuccinimidyl carbonate. The above procedure gives polyanhydrides as intermediates.
An organic group Y having a valence of 2 and having 6 to 40, which is suitable for the reaction with the polyanhydride obtained in the above-described manner 1 In addition to diamines from the above-listed structures, examples thereof include p-phenylenediamine, m-phenylenediamine, 4-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, and the like 4,4' -diaminodiphenyl sulfide, 3' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone 4,4' -diaminodiphenyl sulfide, 3,4' -diaminodiphenyl sulfide 3,3' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone Aminodiphenylmethane, 3,4 '-diaminodiphenylmethane, 3' -diaminodiphenylmethane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [ 4- (4-aminophenoxy) phenyl ] sulfone, bis [ 4- (3-aminophenoxy) phenyl ] sulfone, 4-bis (4-aminophenoxy) biphenyl, 4-bis (3-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl ] ether, bis [ 4- (3-aminophenoxy) phenyl ] ether 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 9, 10-bis (4-aminophenyl) anthracene, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 2-bis [ 4- (4-aminophenoxy) phenyl ] hexafluoropropane, 1, 4-bis (3-aminopropyl dimethylsilyl) benzene, o-tolylsulfone, 9-bis (4-aminophenyl) fluorene, bis {4- (4-aminophenoxy) phenyl } ketone; and compounds in which a part of hydrogen atoms on the benzene ring is substituted with an alkyl chain such as methyl or ethyl, for example, 2 '-dimethyl-4, 4' -diaminodiphenylmethane, 3 '-dimethoxy-4, 4' -diaminobiphenyl, and 3,3 '-dichloro-4, 4' -diaminobiphenyl; and mixtures of these, and the like. However, the diamines are not limited to these. These may be used alone, or 2 or more kinds may be used in combination.
In order to improve adhesion between the photosensitive resin layer formed on the substrate by applying the photosensitive resin composition to the substrate and various substrates, diaminosiloxanes such as 1, 3-bis (3-aminopropyl) tetramethyldisiloxane and 1, 3-bis (3-aminopropyl) tetraphenyldisiloxane may be copolymerized in the preparation of the polyimide precursor (a).
As a method of introducing a reactive substituent to the end of the main chain, a method described below can be mentioned. First, in the amide polycondensation, for example, diamine is excessively added to make amino groups at both ends of the main chain. Then, a compound having a reactive substituent which reacts with heat or light and having a site which also reacts with an amino group is reacted with the amino group. In this case, examples of the site to be reacted with the amino group include an acid anhydride, an epoxy, and an isocyanate. In addition, can alsoThe following methods are exemplified. First, a partially esterified tetracarboxylic acid is excessively added at the time of amide polycondensation, so that both ends of the main chain are carboxyl groups. Then, a compound having a reactive substituent which reacts with heat or light and having a site which also reacts with the carboxyl group is reacted with the carboxyl group. In this case, examples of the site reacting with the carboxyl group include an amine, an alcohol, and the like. Further, as other synthetic methods, the following methods are exemplified: the esterified tetracarboxylic acid having a terminal structure is synthesized first, and then an amide polycondensation with a diamine is performed, thereby obtaining the product. The following methods can be exemplified: by reacting the desired organic radical X having a valence of 4 1 A method of reacting a tetracarboxylic dianhydride having an isocyanate group with an alcohol having a photopolymerizable group (for example, an unsaturated double bond) to thereby produce a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester); by reacting the desired organic radical X having a valence of 4 1 A method of producing a partially esterified tetracarboxylic acid (hereinafter also referred to as acid/ester) by reacting a tetracarboxylic dianhydride with an alcohol having a photopolymerizable group (for example, an unsaturated double bond) and then reacting the resultant tetracarboxylic dianhydride with a compound having an isocyanate group. Optionally, a saturated aliphatic alcohol may be used in combination with the above-mentioned alcohol having a photopolymerizable group.
Examples of the compound having a reactive substituent which reacts with heat or light and having a site which reacts with an amino group to introduce the reactive substituent into the terminal of the main chain include maleic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride, itaconic anhydride, methacrylic anhydride, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-ethynylphthalic anhydride, 4-vinylphthalic anhydride, and di-t-butyl dicarbonate. Examples of the compound having a reactive substituent which reacts with heat or light and having a site which also reacts with a carboxyl group include 4-aminostyrene and 4-ethynylaniline.
After the completion of the amide polycondensation reaction, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid may be filtered off as needed, and then a suitable poor solvent such as water, an aliphatic lower alcohol, a mixed solution thereof or the like may be added to the solution containing the polymer component to precipitate the polymer component, and then the operations such as redissolution and reprecipitation precipitation operations may be repeated as needed to purify the polymer, followed by vacuum drying, thereby separating the target polyimide precursor. In order to improve the degree of purification, the solution of the polymer may be passed through a column in which an anion and/or cation exchange resin is swollen with a suitable organic solvent and packed, to remove ionic impurities.
The weight average molecular weight of the polyimide precursor (a) is preferably 8,000 ～ 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 ～ 40,000, when measured as a polystyrene equivalent weight average molecular weight by Gel Permeation Chromatography (GPC), from the viewpoints of heat resistance and mechanical properties of a film obtained after heat treatment. When the weight average molecular weight is 8,000 or more, it is preferable because of good mechanical properties, and when it is 150,000 or less, it is preferable because of good dispersibility in a developer and resolution of relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight can be determined from a standard curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from among organic solvent-based standard samples STANDARD SM-105 manufactured by Showa electric company.
[ (B) photopolymerization initiator ]
(B) The photopolymerization initiator is a compound capable of generating radicals by active light and polymerizing an ethylenically unsaturated group-containing compound or the like. Examples of the initiator that generates radicals by the active light include compounds having a structure such as benzophenone, N-alkylaminoacetophenone, oxime ester, acridine, and phosphine oxide. Examples thereof include benzophenone, N, N, N ', N ' -tetramethyl-4, 4' -diaminobenzophenone (Michler's ketone), N, N, N ', aromatic ketones such as N ' -tetraethyl-4, 4' -diaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, and the like; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzin, and ethylbenzoin; oxime ester compounds such as 1, 2-octanedione, 1- [4- (phenylthio) -,2- (O-benzoyl oxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime) (manufactured by BASF JAPAN corporation, irgacure Oxe 02), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyl oxime) (manufactured by the company of strong electronic materials, PBG305, 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyl oxime) (TR-PBG-326 manufactured by liking chemical company); benzil derivatives such as benzil dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1, 7-bis (9, 9' -acridinyl) heptane; n-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; an oxazole compound; phosphine oxide compounds such as 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, but are not limited thereto. The polymerization initiator (C) described above may be used alone or in combination of 2 or more. Among the photopolymerization initiators, oxime ester compounds are more preferable from the viewpoint of resolution in particular. Of these, radical species derived from methyl groups are particularly preferred.
The amount of the photopolymerization initiator to be blended is 0.5 parts by mass or more and 10 parts by mass or less, preferably 1 part by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (a). The blending amount is preferably 0.5 parts by mass or more from the viewpoint of photosensitivity or patterning property, and 10 parts by mass or less from the viewpoint of physical properties of the photosensitive resin layer after curing the photosensitive resin composition.
[ (C) solvent ]
(C) The solvent is not limited as long as it can uniformly dissolve or suspend the (a) polyimide precursor and the (B) photopolymerization initiator. Examples of such solvents include γ -butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N-dimethylacetamide, ε -caprolactone, 1, 3-dimethyl-2-imidazolidone, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N, N-dimethylacetamide. These solvents may be used alone or in combination of 2 or more.
The solvent may be used in a range of, for example, 30 to 1500 parts by mass, preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the polyimide precursor (a), depending on the desired coating film thickness and viscosity of the photosensitive resin composition. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, and when 50% by mass or less, the solubility of the polyimide precursor (a) is improved.
[ (D) silane coupling agent ]
In order to improve the adhesion of the relief pattern, the photosensitive resin composition may optionally contain (D) a silane coupling agent. (D) The silane coupling agent preferably has a structure represented by the following general formula (12).
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{ in which R 12 Is at least 1 selected from the group consisting of substituents comprising epoxy, phenylamino, ureido, isocyanato and ureido, R 13 Each independently is an alkyl group having 1 to 4 carbon atoms, R 14 Is hydroxy or alkyl with 1-4 carbon atoms, d is an integer of 1-3, m 8 Is an integer of 1 to 6. }
In the general formula (12), d is not limited as long as d is an integer of 1 to 3, and is preferably 2 or 3, more preferably 3, from the viewpoint of adhesion to a metal rewiring layer or the like. m is m 8 The integer of 1 to 6 is not limited, but is preferably 1 to 4 from the viewpoint of adhesion to the metal rewiring layer. From the viewpoint of developability, it is preferably 2 or more and 5 or less.
R 12 The substituent is not limited as long as it is a substituent containing any structure selected from the group consisting of an epoxy group, a phenylamino group, an ureido group, an isocyanato group and an ureido group. Among these, from the viewpoints of developability and adhesion of the metal rewiring layer, at least 1 selected from the group consisting of a substituent containing a phenylamino group, a substituent containing an ureido group, and a substituent containing an ureido group is preferable, and a substituent containing a phenylamino group is more preferable. R is R 13 The alkyl group having 1 to 4 carbon atoms is not limited. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like. R is R 14 The hydroxyl group or the alkyl group having 1 to 4 carbon atoms is not limited. Examples of the alkyl group having 1 to 4 carbon atoms include the same as R 13 The same alkyl group.
Examples of the epoxy group-containing silane coupling agent include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropyl methyldimethoxysilane, 3-epoxypropoxypropyl trimethoxysilane, 3-epoxypropoxypropyl methyldiethoxysilane, and 3-epoxypropoxypropyl triethoxysilane. As the phenylamino group-containing silane coupling agent, N-phenyl-3-aminopropyl trimethoxysilane is exemplified. As the ureido group-containing silane coupling agent, 3-ureidopropyl trialkoxysilane can be exemplified. As the silane coupling agent containing an isocyanate group, 3-isocyanatopropyltriethoxysilane can be exemplified.
[ (E) radical polymerizable Compound ]
In order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain (E) a radical polymerizable compound. The (meth) acrylic compound which is preferably subjected to a radical polymerization reaction by a photopolymerization initiator is not particularly limited to the following, but examples thereof include ethylene glycol or polyethylene glycol mono-or di-acrylic acid or methacrylic acid esters represented by diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, propylene glycol or polypropylene glycol mono-or di-acrylic acid or methacrylic acid esters, glycerol mono-, di-or tri-acrylic acid or methacrylic acid esters, cyclohexane diacrylate or dimethacrylate, 1, 4-butanediol diacrylate or dimethacrylate, 1, 6-hexanediol diacrylate or dimethacrylate, neopentyl glycol diacrylate or dimethacrylate, bisphenol A mono-or di-acrylic acid or methacrylic acid esters, trimethacrylate, isobornyl acrylate or methacrylic acid esters, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate or methacrylate esters, glycerol di-or triacrylate or methacrylic acid esters, pentaerythritol di-, tri-or tetraacrylate or methacrylic acid esters, ethylene oxide or propylene oxide adducts of these compounds, and the like. These monomers may be used in 1 kind, or may be used in a mixture of 2 or more kinds.
The compounding amount of the compound having an ethylenically unsaturated double bond is 0.5 to 15 parts by mass relative to 100 parts by mass of the polyimide precursor (A).
[ (F) thermal crosslinking agent ]
In order to improve the chemical resistance of the cured film, the photosensitive resin composition may optionally contain (F) a thermal crosslinking agent.
(F) The thermal crosslinking agent is a compound which undergoes an addition reaction or a polycondensation reaction by heat. These reactions occur between (a) the resin and (F) the thermal crosslinking agent, (F) the thermal crosslinking agent each other, and (F) the combination of the thermal crosslinking agent and other components described later, and the reaction temperature is preferably 150 ℃.
(F) The thermal crosslinking agent preferably contains nitrogen atoms. This improves the interaction with the polyimide resin, and thus, higher chemical resistance can be expected. Examples of the thermal crosslinking agent (F) include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, blocked isocyanate compounds, and the like.
Examples of the alkoxymethyl compound include, but are not limited to, the following compounds.
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Examples of the epoxy compound include an epoxy compound containing a bisphenol A group, hydrogenated bisphenol A diglycidyl ether (for example, epoligo 4000 manufactured by Kagaku chemical Co., ltd.), and the like. Examples of oxetane compounds include 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, bis [ 1-ethyl (3-oxetanyl) methyl ] ether, 4 '-bis [ (3-ethyl-3-oxetanyl) methyl ] biphenyl, 4' -bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenolate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, poly [ [3- [ (3-ethyl-3-oxetanyl) methoxy ] propyl ] silsesquioxane ] derivative, oxetanyl silicate, phenol novolac oxetane, 1, 3-bis [ (3-ethyl-oxetan-3-yl) methoxy ] benzene, and (trade name) synthesized (trade name) such as east (trade name) and east (trade name) system (trade name) 221). Examples of the bismaleimide compound include 1, 2-bis (maleimide) ethane, 1, 3-bis (maleimide) propane, 1, 4-bis (maleimide) butane, 1, 5-bis (maleimide) pentane, 1, 6-bis (maleimide) hexane, 2, 4-trimethyl-1, 6-bis (maleimide) hexane, N '-1, 3-phenylene bis (maleimide), 4-methyl-N, N' -1, 3-phenylene bis (maleimide), N '-1, 4-phenylene bis (maleimide), 3-methyl-N, N' -1, 4-phenylene bis (maleimide), 4 '-bis (maleimide) diphenylmethane, 3' -diethyl-5, 5 '-dimethyl-4, 4' -bis (maleimide) diphenylmethane and 2, 2-bis [4- (4-maleimide phenoxy) phenyl ] propane. Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-acryloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallylisocyanurate, triallylcyanurate, triallylamine, triallylcarboxylate 1,3, 5-trimellitate, triallylphosphate, triallylphosphite, and triallylcitrate. Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (for example, duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B and WM44-L70G, takenate B-882N, baxenden, inc., 7960, 7961, 7982, 7991 and 7992, manufactured by Sanyo chemical Co., ltd.), toluene diisocyanate-based blocked isocyanates (for example, takenate B-830, manufactured by Sanyo chemical Co., ltd.), 4' -diphenylmethane diisocyanate-based blocked isocyanates (for example, takenate B-815N, manufactured by Sanyo chemical Co., ltd.), 1, 3-BIs (isocyanatomethyl) cyclohexane-based blocked isocyanates (for example, takenate B-846, toku Kagaku, takenate B-830, etc.), takenate-2507, cork.g., takenate B-7954, etc.), and PMD (for example, manufactured by Sanyo chemical Co., ltd.) and PMD.257950, etc. Among these, blocked isocyanate and bismaleimide compounds are preferable from the viewpoint of storage stability. (F) The thermal crosslinking agent may be used alone, or 2 or more may be used in combination.
The content of the thermal crosslinking agent (F) in the resin composition is 0.2 to 40% by mass, more preferably 1 to 20% by mass, and still more preferably 2 to 10% by mass, based on the total solid content of the resin composition, from the viewpoints of low dielectric characteristics and chemical resistance.
[ (G) Filler ]
In order to improve the chemical resistance of the cured film, the photosensitive resin composition may optionally contain (G) a filler. The filler is not limited as long as it is an inactive substance added to improve strength and various properties.
The filler is preferably in the form of particles from the viewpoint of suppressing the increase in viscosity when the resin composition is produced. Examples of the particles include needles, plates, and spheres, and the filler is preferably spheres from the viewpoint of suppressing the increase in viscosity when the resin composition is produced.
Examples of the needle-like filler include wollastonite, potassium titanate, xonotlite, aluminum borate, and needle-like calcium carbonate.
Examples of the platy filler include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, platy calcium carbonate, and the like.
Examples of the spherical filler include calcium carbonate, silica, alumina, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, and barium titanate. Among these, silica, alumina, titanium oxide, and barium titanate are preferable from the viewpoints of electrical characteristics and storage stability when a resin composition is produced, and silica and alumina are more preferable.
The filler size is defined as the primary particle diameter when spherical, and the length of the long side is defined as the filler size when plate-like or needle-like, and is preferably 5nm to 1000nm, more preferably 10nm to 1000nm. When the particle size is 10nm or more, the resin composition tends to be sufficiently uniform, and when the particle size is 1000nm or less, photosensitivity can be imparted. From the viewpoint of imparting photosensitivity, it is preferably 800nm or less, more preferably 600nm or less, particularly preferably 300nm or less. From the viewpoints of adhesion and uniformity of the resin composition, the particle size is preferably 15nm or more, more preferably 30nm or more, and particularly preferably 50nm or more.
The content of the filler (G) in the resin composition is 1 to 20vol%, preferably 5 to 20vol% from the viewpoint of dielectric characteristics, and more preferably 5 to 10vol% from the viewpoint of resolution, based on the mass of the resin composition.
[ other Components ]
The photosensitive resin composition may further contain components other than the above components (a) to (G). Examples of the other components include: a resin component other than the polyimide precursor (A); an organic compound containing a metal element, a sensitizer, a thermal polymerization inhibitor, an azole compound, a hindered phenol compound, and the like.
The photosensitive resin composition may further contain a resin component other than the polyimide precursor (a). Examples of the resin component that can be contained in the photosensitive resin composition include polyimide, polyoxazole precursor, phenol resin, polyamide, epoxy resin, silicone resin, and acrylic resin. The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (a).
The photosensitive resin composition may contain an organic compound containing a metal element. The organic compound containing a metal element preferably contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule. The organic group preferably includes a hydrocarbon group and a heteroatom-containing hydrocarbon group. By containing the organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition is increased, and the dielectric loss tangent of the cured film is reduced. Examples of the organic titanium or zirconium compound that can be used include compounds in which an organic group is bonded to a titanium atom or a zirconium atom by covalent bond or ionic bond.
Specific examples of the organic titanium or zirconium compound are shown in the following I) to VII):
The chelate compound of I) is more preferably a compound having 2 or more alkoxy groups from the viewpoint of storage stability of the photosensitive resin composition and obtaining a good pattern. Specific examples of the chelate compound include titanium bis (triethanolamine) diisopropoxide, titanium di-n-butoxybis (2, 4-pentanedione), titanium diisopropoxide bis (tetramethylheptanedione), titanium diisopropoxide bis (ethylacetoacetate), and compounds in which a titanium atom of these compounds is replaced with a zirconium atom, but are not limited thereto.
Examples of the (II) tetraalkoxy compound include titanium tetra (n-butoxy), titanium tetraethoxide, titanium tetra (2-ethylhexyloxy) titanium, titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonyloxy) titanium, titanium tetra (n-propoxy) titanium, titanium tetrastearyloxy, titanium tetra [ bis {2,2- (allyloxymethyl) butoxy } ], and compounds in which the titanium atom of these compounds is replaced with a zirconium atom.
Examples of the III) titanocene or zirconocene compound include trimethoxypenta cyclopentadienyl titanium, bis (. Eta.5-2, 4-cyclopentadienyl-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta.5-2, 4-cyclopentadienyl-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and compounds in which a titanium atom of these compounds is replaced with a zirconium atom.
Examples of the monoalkoxy compound IV) include titanium isopropoxide (dioctyl phosphate), titanium isopropoxide (dodecylbenzenesulfonyl), and a compound obtained by substituting a zirconium atom for a titanium atom of these compounds, but are not limited thereto.
Examples of the V) titanium oxide or zirconium oxide compound include, but are not limited to, bis (pentanedione) titanium oxide, bis (tetramethyl heptanedione) titanium oxide, oxytitanium phthalocyanine, and compounds in which the titanium atom of these compounds is replaced with a zirconium atom.
Examples of the VI) titanium tetra-acetylacetonate or zirconium tetra-acetylacetonate compound include titanium tetra-acetylacetonate and a compound obtained by substituting a zirconium atom with a titanium atom of these compounds, but are not limited thereto.
Examples of the VII) titanate coupling agent include isopropyl tris (dodecylbenzenesulfonyl) titanate, but are not limited thereto.
In the above I) to VII), the organic titanium compound is preferably at least 1 compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound from the viewpoint of exhibiting a more excellent dielectric loss tangent. Particularly preferred are diisopropoxybis (ethylacetoacetate) titanium, tetra (n-butoxy) titanium and bis (. Eta.) 5 -2, 4-cyclopentadienyl-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.
The amount of the organic titanium or zirconium compound to be compounded is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the (a) resin. When the amount of the resin composition is 0.01 parts by mass or more, the resin composition exhibits a good imidization ratio and dielectric loss tangent of a cured film, and when it is 10 parts by mass or less, the resin composition is excellent in storage stability, and therefore is preferable.
The photosensitive resin composition can increase the imidization rate of the polyimide precursor contained in the resin composition and reduce the dielectric loss tangent of a cured film using the resin composition by containing the organic compound containing a metal element. While not being bound by theory, it is believed that the reason for increasing the imidization rate of polyimide precursors is: the metal element contained in the organic compound containing the metal element coordinates to the carbonyl group of the ester group and/or the carboxyl group derived from the polyimide precursor, thereby reducing the electron density of the carbon atom of the carbonyl group and promoting the ring-closure reaction.
The photosensitive resin composition may optionally contain a sensitizer in order to increase sensitivity. As a sensitizer which is used for the preparation of the dye, examples thereof include milone, 4 '-bis (diethylamino) benzophenone, 2, 5-bis (4' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 '-diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4' -diethylaminobenzylidene) -4-methylcyclohexanone, 4 '-bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenyl-biphenylene) -benzothiazole, 2- (p-dimethylaminophenyl-vinylene) benzothiazole, and 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1, 3-bis (4 '-dimethylaminobenzylidene) acetone, 1, 3-bis (4' -diethylaminobenzylidene) acetone, 3 '-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzoyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like. These may be used singly or in combination of plural kinds (e.g., 2 to 5 kinds). The compounding amount of the sensitizer is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the polyimide precursor (a).
In particular, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor in order to improve the stability of viscosity and sensitivity of the photosensitive resin composition when stored in a solution containing a solvent. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenyl naphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenyl hydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt, and the like can be used. In addition, 1 kind of these thermal polymerization inhibitors may be used, or a mixture of 2 or more kinds may be used. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 to 12 parts by mass based on 100 parts by mass of the polyimide precursor (a).
When a substrate containing copper or a copper alloy is used, the photosensitive resin composition may optionally contain an azole compound in order to suppress discoloration of the substrate. As the azole compound, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4, 5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyl-triazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyl-triazole, 1, 5-dimethyltriazole, 4, 5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [ 2-hydroxy-3, 5-bis (. Alpha.,. Alpha. -dimethylbenzyl) phenyl ] -benzotriazole, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole, 2- (3, 5-di-t-hydroxyphenyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-phenyl-benzotriazole, 2' -hydroxy-2-hydroxyphenyl-benzotriazole, 2' -hydroxy-phenyl-benzotriazole, 2- (2, 5-hydroxy-methylphenyl) benzotriazole, 2-hydroxy-methyl-2 ' -hydroxy-benzotriazole, 2-hydroxy-phenyl-benzotriazole, 2-hydroxy-methyl-2-hydroxy-benzotriazole, 2-hydroxy-1-hydroxy-benzotriazole, 2-methyl-hydroxy-1-hydroxy-benzotriazole, 2-methyl-1-hydroxy-phenyl-benzotriazole, 2-hydroxy-1-hydroxy-phenyl-benzotriazole, and 2-hydroxy-phenyl-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like. Tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole are particularly preferred. These azole compounds may be used in 1 kind or in a mixture of 2 or more kinds.
The amount of the azole compound to be blended is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, from the viewpoint of sensitivity characteristics, relative to 100 parts by mass of the polyimide precursor (a). When the amount of the azole compound to be blended is 0.1 part by mass or more based on 100 parts by mass of the polyimide precursor (a), discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or copper alloy, and on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent, and therefore, it is preferable.
When a substrate containing copper or a copper alloy is used, the photosensitive resin composition may contain a hindered phenol compound in order to suppress discoloration of the substrate. Examples of the hindered phenol compound include octadecyl 3- (3, 5-di-t-butyl-4-methylphenol, octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 4' -methylenebis (2, 6-di-t-butylphenol), 4' -thio-bis (3-methyl-6-t-butylphenol), 4' -butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [ 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [ 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2-thio-diethylenebis [ 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], N ' -hexamethylenebis (3, 5-di-t-butyl-4-hydroxy-cinnamide), 2, 4' -di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol, and pentaerythritol-bis [ 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3-hydroxy-2, 6-dimethyl-4-isopropylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris [4- (1-ethylpropyl) -3-hydroxy-2, 6-dimethylbenzyl ] -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris [ 4-triethylmethyl-3-hydroxy-2, 6-dimethylbenzyl ] -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (3-hydroxy-2, 6-dimethyl-4-phenylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 5, 6-trimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-5-ethyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione 1,3, 5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2, 5-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-5, 6-diethyl-3-hydroxy-2-methylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 5-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 1,3, 5-tris (4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3, 5-triazine-2, 4,6- (1 h,3h,5 h) -trione, and the like, but are not limited thereto. Of these, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1 h,3h,5 h) -trione is particularly preferred.
The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, from the viewpoint of sensitivity characteristics, relative to 100 parts by mass of the (a) polyimide precursor. When the compounding amount of the hindered phenol compound is 0.1 part by mass or more with respect to 100 parts by mass of the polyimide precursor (a), for example, when the photosensitive resin composition is formed on copper or copper alloy, discoloration and corrosion of copper or copper alloy can be prevented, and when it is 20 parts by mass or less, the sensitivity is excellent, and thus, it is preferable.
Polyimide cured film and method for producing the same
The present disclosure also provides a method for producing a polyimide cured film, which includes a step of converting a photosensitive resin composition into polyimide. The method for producing a polyimide cured film of the present disclosure includes, for example, the following steps (1) to (5):
(1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition of the present disclosure to the substrate;
(2) A step of heating and drying the photosensitive resin layer obtained;
(3) Exposing the heated and dried photosensitive resin layer to light;
(4) Developing the exposed photosensitive resin layer; a kind of electronic device with high-pressure air-conditioning system
(5) And a step of forming a polyimide cured film by heat-treating the developed photosensitive resin layer.
The photosensitive resin composition used in the method for producing a cured film preferably contains 100 parts by mass of a polyimide precursor, 0.5 to 10 parts by mass of a photosensitive agent, and 100 to 300 parts by mass of a solvent, more preferably contains a photo radical polymerization initiator as the photosensitive agent, and still more preferably the photosensitive resin composition is negative.
The specific steps in the method for producing a cured film may be performed according to steps (1) to (5) of the method for producing a cured film described above. A typical mode of each step will be described below.
(1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition to the substrate
In this step, the photosensitive resin composition of the present disclosure is applied to a substrate, and then dried as necessary to form a photosensitive resin layer. As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, a method of spray coating with a spray coater, or the like can be used.
(2) A step of heating and drying the photosensitive resin layer
The photosensitive resin composition film may be heated and dried, as necessary. As the drying method, a method such as air drying, heat drying by an oven or a hot plate, vacuum drying, or the like can be used. Further, it is desirable to dry the coating film under such conditions that imidization of the (a) polyimide precursor (polyamic acid ester) in the photosensitive resin composition is not caused. Specifically, when air-drying or heat-drying is performed, the drying may be performed at 20 to 140℃for 1 minute to 1 hour. By the above operation, a photosensitive resin layer can be formed on the substrate.
(3) Exposing the heated and dried photosensitive resin layer to light
In this step, the photosensitive resin layer formed in the above is exposed. As the exposure device, for example, a contact aligner, mirror projection, stepper, or the like is used. The exposure may be performed via a patterned photomask or reticle or directly. The light used for exposure is, for example, an ultraviolet light source.
After exposure, for the purpose of improving the sensitivity and the like, post-exposure baking (PEB) and/or pre-development baking may be performed at an arbitrary combination of temperature and time as needed. The baking conditions are preferably in the range of 40 to 120℃and the time is preferably in the range of 10 to 240 seconds, but the present invention is not limited to this range as long as the properties of the negative photosensitive resin composition are not inhibited.
(4) Developing the exposed photosensitive resin layer
In this step, the photosensitive resin layer after exposure is developed to form a relief pattern. When the photosensitive resin composition is negative, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from conventionally known developing methods for photoresists, for example, a spin spray method, a paste plate method, a dipping method accompanied by ultrasonic treatment, and the like. Further, after development, post-development baking may be performed at any combination of temperature and time as needed for the purpose of adjusting the shape of the relief pattern or the like. As the developing solution used for development, for example, a good solvent for the negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. Examples of the good solvent include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, cyclopentanone, cyclohexanone, gamma-butyrolactone, and alpha-acetyl-gamma-butyrolactone. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When the poor solvent is used in combination with the poor solvent, the ratio of the poor solvent to the poor solvent is preferably adjusted according to the solubility of the polymer in the negative photosensitive resin composition. In addition, 2 or more solvents may be used in combination, for example, in plural. In the step of developing the photosensitive resin layer after exposure, the coating and developing steps are preferably performed so as to obtain a photosensitive resin layer having a thickness of 10 μm to 15 μm. The development time is preferably 30 seconds or less, more preferably 25 seconds or less, and still more preferably 20 seconds or less. While not being bound by theory, the development time is set to 30 seconds or less, which causes a difference in solubility with the exposed portion, thereby imparting contrast and improving the resolution of the pattern.
(5) A step of forming a polyimide cured film by heat-treating the developed photosensitive resin layer
In this step, the relief pattern obtained by the development is heated to volatilize the photosensitive component, and the polyimide precursor (a) is imidized to convert it into a cured relief pattern formed of polyimide. As a method of heat curing, various methods such as a method using a hot plate, a method using an oven, a method using a temperature-raising oven capable of setting a temperature program, and the like can be selected. The heating may be performed, for example, at 160℃to 400℃for 30 minutes to 5 hours. As an atmosphere gas at the time of heat curing, air may be used, or an inert gas such as nitrogen or argon may be used. Thereby, a cured relief pattern (polyimide cured film) can be produced.
The method for producing a cured polyimide film of the present disclosure is, for example, a method for producing a cured film comprising applying the photosensitive resin composition of the present disclosure to a substrate, performing an exposure treatment, a development treatment, and then performing a heating treatment, and the cured film preferably has a dielectric loss tangent of 0.003 to 0.012 when measured at 40GHz by a perturbed split-cylinder resonator method. The dielectric loss tangent can be measured by a perturbed split cylindrical resonator method shown in examples described below.
The present disclosure also provides a polyimide cured film obtained from the photosensitive resin composition described above. The moisture permeability of the cured film is preferably less than 800, more preferably less than 700. The lower the moisture permeability, the less the frequency dependence of the dielectric loss tangent tends to be, and therefore, good from the viewpoint of dielectric loss tangent, while the lower the moisture permeability, the poorer the solubility of the unexposed portion at the time of patterning, and the resolution is deteriorated, and therefore, more preferably 500 or more and less than 800. By less than 800, a cured film with high reliability can be obtained. For details of the method for measuring the moisture permeability, please refer to the following. From the viewpoint of resolution, dielectric characteristics and frequency dependence of dielectric loss tangent, the product of dielectric loss tangent and moisture permeability (tan delta) is preferable 40 X WVTR) is in a certain fixed range, and when a dielectric loss tangent of 40GHz is used, the following formula (3) is preferably satisfied.
3.0＜tanδ 40 ×WVTR＜10.0(3)
By bringing tan delta 40 The XWVTR is in the range of 3.0 to 10.0, and a polyimide cured product having excellent resolution and dielectric characteristics and little frequency dependence can be obtained. The difference in dielectric loss tangent between 40GHz and 10GHz is preferably 0.0015 or less, and more preferably 0.001 or less.
Regarding the substrate forming the cured relief pattern manufactured using the present disclosure, it is preferably formed on a substrate selected from the group consisting of resin, silicon (Si), copper (Cu), aluminum (Al), and combinations of these, preferably on Cu. When forming a cured relief pattern on Cu, it may be formed on a Cu layer formed on a Si wafer. Other metal layers may be formed between the Si wafer and the Cu layer. The metal layer formed between the Si wafer and the Cu layer is preferably a Ti layer.
The aspect ratio of the cured relief pattern is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. By increasing the aspect ratio, finer wirings can be formed. In the case of forming a cured film having a thickness of 10 μm, for example, the minimum opening size of the through hole is preferably a through hole having an opening of 20 μm or less, more preferably a through hole having an opening of 15 μm or less, and still more preferably a through hole having an opening of 10 μm or less.
Semiconductor device
The present disclosure may also provide a semiconductor device having a cured relief pattern obtained by the above-described method for manufacturing a cured relief pattern using the photosensitive resin composition of the present disclosure. Accordingly, a semiconductor device having a substrate as a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the cured relief pattern manufacturing method described above is provided. The present disclosure is also applicable to a method for manufacturing a semiconductor device using a semiconductor element as a base material and including the method for manufacturing a cured relief pattern as part of a process. The semiconductor device may be manufactured as follows: the cured relief pattern formed by the above-described method for producing a cured relief pattern is formed as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, a protective film for semiconductor devices having bump structures, or the like, and is produced in combination with a known method for producing semiconductor devices.
The polyimide contained in the cured relief pattern (polyimide cured film) formed from the polyimide precursor composition preferably has a structure represented by the following general formula (13).
{ in the general formula (13), X 1 Y and Y 1 X is the same as X in the above general formula (4) 1 Y and Y 1 Identical, and n 2 Is an integer of 2 to 150. }
< display device >)
The present disclosure may also provide a display device using the photosensitive resin composition of the present disclosure, and including a display element and a cured film provided on an upper portion of the display element, the cured film being the cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element or may be laminated with other layers interposed therebetween. Examples of the cured film include surface protective films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA liquid crystal display devices, and barrier ribs for cathodes of organic EL elements.
The photosensitive resin composition of the present disclosure is useful for applications such as interlayer insulation of a multilayer circuit, coverlay coating of a flexible copper clad laminate, solder resist, liquid crystal alignment film, and the like, in addition to applications in the above-described semiconductor device.
Examples
Physical properties of the photosensitive resin compositions in examples, comparative examples and production examples of the present disclosure were measured and evaluated by the following methods.
[ measurement and evaluation method ]
(1) Weight average molecular weight
The weight average molecular weight (Mw) of each photosensitive resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used in the measurement was Shodex 805M/806M manufactured by Showa electric company, shodex STANDARD SM-105 manufactured by Showa electric Co., ltd., standard monodisperse polystyrene was selected, N-methyl-2-pyrrolidone was used as the developing solvent, and Shodex RI-930 manufactured by Showa electric company was used as the detector.
(2) Resolution and development time of cured relief pattern on Cu substrate
A6-inch silicon wafer (manufactured by Fujim electronic industries Co., ltd., thickness: 625.+ -. 25 μm) was successively sputtered with Ti having a thickness of 200nm and Ti having a thickness of 400nm using a sputtering apparatus (manufactured by L-440S-FHL, manufactured by Canon Anelva Corporation)Is a Cu of (3). Next, a photosensitive resin composition prepared by a method described below was Spin-coated on the wafer using a Coater Developer (D-Spin 60A type, manufactured by SOKUDO Co.) and dried by heating on a hot plate at 110℃for 3 minutes, thereby forming a photosensitive resin layer having a thickness of about 13.5. Mu.m. On the photosensitive resin layer, 200mJ/cm was irradiated with prism GHI (Ultratech Co.) equipped with an i-ray filter using a mask with a test pattern 2 Is a function of the energy of the (c). Next, this photosensitive resin layer was subjected to spray development with a Coater Developer (D-Spin 60A type, manufactured by SOKUDO corporation) using cyclopentanone as a Developer, and rinsed with propylene glycol methyl ether acetate, thereby obtaining a relief pattern on Cu. The time of spray development at this time was defined as development time. The wafer having the relief pattern formed on Cu was subjected to a heat treatment at 230 ℃ for 2 hours in a nitrogen atmosphere using a temperature-programmed curing oven (model VF-2000, manufactured by Koyo Lindbergh co., ltd.) to obtain a cured relief pattern of resin having a thickness of about 10 μm on Cu. The embossed pattern thus produced was observed under an optical microscope, and the minimum opening pattern size of the through-hole was obtained. In this case, if the area of the opening of the obtained pattern is 1/2 or more of the corresponding pattern mask opening area, it is considered that the resolution can be resolved, and the resolution is determined based on the length of the mask opening side (the size of the opening pattern) corresponding to the opening having the smallest area among the resolvable openings, according to the following evaluation criteria.
(evaluation criterion)
A: the minimum opening pattern has a size of less than 10 μm
B: the minimum opening pattern has a size of 10 μm or more and less than 15 μm
C: the minimum opening pattern has a size of 15 μm or more and less than 20 μm
D: the minimum opening pattern has a size of 20 μm or more
(3) Measurement of dielectric Properties (relative permittivity: dk, dielectric loss tangent: df)
A6-inch silicon wafer (manufactured by Fujim electronic industries Co., ltd., thickness: 625.+ -. 25 μm) was sputtered with a sputtering device (manufactured by L-440S-FHL, manufactured by Canon Anelva Corporation) to a thickness of 100nmAluminum (Al), thereby preparing a wafer substrate sputtered with Al. The photosensitive resin composition prepared by the method described later was spin-coated on the above-mentioned Al-sputtered wafer substrate by a spin coater (D-spin 60A type, manufactured by SOKUDO Co.) and dried by heating at 110℃for 180 seconds, thereby forming a photosensitive resin layer having a thickness of about 13.5. Mu.m. Then, the exposure was carried out at 600mJ/cm using a positioner (PLA-501F, manufactured by Canon Co., ltd.) 2 The entire surface of the resultant was exposed to light, and a cured film of a resin was produced on an Al wafer to a thickness of about 10 μm by performing a heat curing treatment in a vertical curing oven (Koyo Lindbergh Co., ltd., model name VF-2000B) at 230℃for 2 hours under a nitrogen atmosphere. The cured film was cut into a length of 80mm, a width of 62mm (for 10GHz measurement) and a length of 40mm, a width of 30mm (for 40GHz measurement) by a cutter (manufactured by DISCO, model name DAD-2H/6T), and then immersed in a 10% aqueous hydrochloric acid solution to peel off the film from the silicon wafer, thereby obtaining a film sample. After the film samples were dried in an oven at 50℃for 24 hours, the relative dielectric constants (Dk) and dielectric loss tangents (Df) at 10GHz and 40GHz were measured, respectively, for the film samples by a resonator perturbation method. The details of the measurement method are as follows.
(measurement method)
Disturbance type split cylinder resonator method
(device constitution)
Network analyzer:
PNA Network analyzer N5224B
(KEYSIGHT Co., ltd.)
Split cylindrical resonator:
CR-710 (measurement frequency: about 10GHz, manufactured by Kanto electronic application development Co., ltd.)
CR-740 (manufactured by Kanto electronic application development Co., ltd., measuring frequency: about 40 GHz)
(4) Moisture permeability test
A wafer substrate on which Al was sputtered was prepared by sputtering 100nm thick aluminum (Al) on a 6-inch silicon wafer (manufactured by Fujimi electronic industries Co., ltd., thickness 625.+ -. 25 μm) using a sputtering apparatus (manufactured by L-440S-FHL, canon Anelva Corporation). A photosensitive resin composition prepared by a method described below was applied to a spin coater (D-spin60A type, manufactured by SOKUDO corporation) was spin-coated on the above-described Al-sputtered wafer substrate, and the substrate was dried by heating at 110 ℃ for 180 seconds, thereby forming a photosensitive resin layer having a thickness of about 13.5 μm. Then, the exposure was carried out at 600mJ/cm using a positioner (PLA-501F, manufactured by Canon Co., ltd.) 2 The entire surface of the resultant was exposed to light, and a cured film of a resin was produced on an Al wafer to a thickness of about 10 μm by performing a heat curing treatment in a vertical curing oven (Koyo Lindbergh Co., ltd., model name VF-2000B) at 230℃for 2 hours under a nitrogen atmosphere. The cured film was cut into a length of 80mm and a width of 62mm by a cutter (manufactured by DISCO, model name DAD-2H/6T), immersed in a 10% aqueous hydrochloric acid solution, and peeled from the silicon wafer to obtain a film sample. The measurement of the moisture permeability was performed based on the cup method of JIS Z0208. The process was carried out under conditions of 40g of calcium chloride and 65℃and 90% RH of moisture permeability. The test was carried out for 24 hours, and then taken out from the constant temperature and humidity machine, left at room temperature for 30 minutes, and weight measurement was carried out. The water permeability (WVTR) is determined by the following calculation formula.
WVTR = { (weight after test) - (weight before test) }/(0.03) 2 X pi) (X)
In the formula X, 0.03 represents the radius (m) of the cup }
The WVTR is a value for a cured film of 10um and depends on the film thickness. For example, when the film thickness is 20um, it is 1/2 of the WVTR value obtained at 10 um. The lower the WVTR value, the lower the water vapor transmission rate of the film. In addition, the more hydrophobic the film, the higher the film density, and the lower the WVTR tends to be.
(5) IR measurement
In the IR measurement, 700cm of the film obtained in the above (3) was measured by the ATR method using Nicolet 380 -1 Above and 4000cm -1 The following ranges were measured at 50 times of scanning. The sample contact uses a silicon prism. For 1450cm -1 1550cm above -1 Absorption peaks in the following ranges were defined as Ph, the maximum peak intensity 1 Setting the second highest peak intensity to Ph 2 Will 1380cm -1 The peak intensity in the vicinity is set to Im 1 Let Ph 1 Is 1 toLine normalization, calculation of Ph 2 And Im 1 . 1380cm -1 The peak intensity in the vicinity was 1380cm -1 ±10cm -1 An inner maximum peak.
[ production of diamine X-1 ]
A5L four-necked flask was replaced with Ar, 172.02g of 4,4' -butylidenebis (6-t-butylm-cresol), 155.84g of 4-chloronitrobenzene and 1.5L of DMF were added thereto and stirred. To which K is added 2 CO 3 186.42g, heated at 150℃for 5 hours, confirm the disappearance of starting material and intermediates by TLC. After cooling to room temperature, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure at 80 ℃. The concentrated residue was poured into 1.6L of ion-exchanged water, followed by adding 2.5L of ethyl acetate thereto, and subjecting to 3-time purification. The organic layer was recovered and MgSO was added 4 Drying is performed. After drying, the mixture was filtered to remove impurities, 800mL of toluene was added to dissolve the mixture, and the resulting solution was added to 4.0L of methanol and stirred for 30 minutes. After stirring, filtration was carried out, and the residue was recovered and dried at 80℃for 12 hours. The dried reaction product was put into a 5L four-necked flask substituted with Ar, and further, 19.04g of 5% Pd/C (EA) and THF1.9L were put thereinto and stirred. The flask was heated to 40℃and H was run 2 Bubbling (10 mL/min) was performed, whereby the reduction reaction was performed for 24 hours. The reaction solution was subjected to celite filtration, and the target fraction was recovered by silica gel column chromatography and concentrated under reduced pressure to give diamine X-1.
[ (A) production of polyimide precursor ]
Synthesis of polyimide precursor (Polymer A-1):
155.1g of 4,4' -oxybisphthalic anhydride (ODPA) was charged into a 2 liter-capacity separable flask, 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of gamma-butyrolactone were added, and 79.1g of pyridine was added while stirring at room temperature, thereby obtaining a reaction mixture. After the exothermic reaction was completed, the reaction mixture was cooled to room temperature and allowed to stand for 16 hours.
Then, a solution of 206.3g of Dicyclohexylcarbodiimide (DCC) dissolved in 180ml of gamma-butyrolactone was added to the reaction mixture with stirring under ice-cooling for 40 minutes, and then a suspension of 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane suspended in 350ml of gamma-butyrolactone was added with stirring for 60 minutes. After stirring for 2 hours at room temperature, 30ml of ethanol was added and stirring was continued for 1 hour, and 400ml of gamma-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 3 liters of ethanol to produce a precipitate containing a crude polymer. The crude polymer thus formed was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was treated with anion exchange resin (ORGANO CORPORATION "cover) TM 15 ") to give a polymer solution. The obtained polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then dried in vacuo to obtain polymer A-1 in the form of a powder. The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 21,000. The polyimide obtained from the polymer A-1 had an imide group concentration U of 19.6% by weight and an aliphatic hydrocarbon group concentration T of 8.4% by weight per repeating unit. The "imide group concentration U" and the "aliphatic hydrocarbon group concentration T" were calculated by converting them into polyimide of a polyimide cured film obtained by heating and curing at 350 ℃ (the same applies hereinafter).
Synthesis of polyimide precursor (Polymer A-2):
polymer A-2 was obtained by the same procedure as described in the synthesis of Polymer A-1, except that 260.2g of 4,4'- (4, 4' -isopropylidenediphenoxy) acid dianhydride was used in place of ODPA155.1g and 92.88g of 2,2 '-dimethylbiphenyl-4, 4' -diamine (m-TB) was used in place of 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane. The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 23,000. The polyimide obtained from the polymer A-2 had an imide group concentration U of 20.1% by weight and an aliphatic hydrocarbon group concentration T of 8.6% by weight per repeating unit.
Synthesis of polyimide precursor (Polymer A-3):
polymer A-3 was obtained by reacting the same procedure as described for the synthesis of Polymer A-1, except that 146.3g of 1, 4-bis (4-aminophenoxy) -2,3, 5-trimethylbenzene was used instead of 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane in the synthesis of Polymer A-1. The weight average molecular weight (Mw) of this polymer A-3 was measured and found to be 20,000. The polyimide obtained from the polymer A-3 had an imide group concentration U of 23.0% by weight and an aliphatic hydrocarbon group concentration T of 7.4% by weight.
Synthesis of polyimide precursor (Polymer A-4):
polymer A-4 was obtained by performing the reaction in the same manner as described in the synthesis of Polymer A-1 except that 147.1g of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1g of ODPA in the synthesis of Polymer A-1. The weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 21,000. The polyimide obtained from the polymer A-4 had an imide group concentration U of 20.1% by weight and an aliphatic hydrocarbon group concentration T of 8.6% by weight.
Synthesis of polyimide precursor (Polymer A-5):
polymer A-5 was obtained by performing the reaction in the same manner as described in the synthesis of Polymer A-1 except that 260.2g of 4,4'- (4, 4' -isopropylidenediphenoxy) acid dianhydride was used instead of the ODPA155.1g in the synthesis of Polymer A-1. The weight average molecular weight (Mw) of this polymer A-5 was measured and found to be 24,000. The polyimide obtained from the polymer A-5 had an imide group concentration U of 15.2% by weight and an aliphatic hydrocarbon group concentration T of 9.8% by weight per repeating unit.
Synthesis of polyimide precursor (Polymer A-6):
in the synthesis of the above-mentioned polymer A-1, a reaction was carried out in the same manner as described in the synthesis of polymer A-1 except that 260.2g of 4,4'- (4, 4' -isopropylidenediphenoxy) acid dianhydride was used in place of 155.1g of ODPA155.2 g, and 176.98g of 1, 4-bis (4-aminophenoxy) -2, 5-di-t-butylbenzene was used in place of 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane, thereby obtaining polymer A-6. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 22,000. The polyimide obtained from the polymer A-6 had an imide group concentration U of 15.8% by weight and an aliphatic hydrocarbon group concentration T of 16.2% by weight.
Synthesis of polyimide precursor (Polymer A-7):
in the synthesis of the above polymer A-1, a reaction was carried out in the same manner as described in the synthesis of polymer A-1 except that 260.2g of 4,4'- (4, 4' -isopropylidenediphenoxy) acid dianhydride was used in place of 155.1g of ODPA155.1 and 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane was used in place of 247.1g of diamine X, to thereby obtain polymer A-7. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 20,000. The polyimide obtained from the polymer A-7 had an imide group concentration U of 13.3% by weight and an aliphatic hydrocarbon group concentration T of 20.7% by weight per repeating unit.
Synthesis of polyimide precursor (Polymer A-8):
in the synthesis of the above-mentioned polymer A-1, a reaction was carried out in the same manner as described in the synthesis of polymer A-1 except that 109.06g of pyromellitic dianhydride was used in place of ODPA150.1g and 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane was used in place of diamine X-1.1 g, whereby polymer A-8 was obtained. The weight average molecular weight (Mw) of this polymer A-8 was measured and found to be 14,000. The polyimide obtained from the polymer A-8 had an imide group concentration U of 18.7% by weight and an aliphatic hydrocarbon group concentration T of 25.1% by weight.
Synthesis of polyimide precursor (Polymer A-9):
polymer A-9 was obtained by performing the reaction in the same manner as described in the synthesis of Polymer A-1 except that instead of 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane, 95.93g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane and 89.8g of 2, 2-bis {4- (4-aminophenoxy) phenyl } propane were used in the synthesis of Polymer A-1. The weight average molecular weight (Mw) of this polymer A-9 was measured and found to be 21,000. The polyimide obtained from the polymer A-9 had an imide group concentration U of 20.0% by weight and an aliphatic hydrocarbon group concentration T of 6.5% by weight per repeating unit.
Synthesis of polyimide precursor (Polymer A-10):
polymer A-10 was obtained by performing the reaction in the same manner as described in the synthesis of Polymer A-1 except that 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane was used instead of 247.1g of diamine X-1 in the synthesis of Polymer A-1. The weight average molecular weight (Mw) of this polymer A-10 was measured and found to be 16,000. The polyimide obtained from the polymer A-10 had an imide group concentration U of 16.7% by weight and an aliphatic hydrocarbon group concentration T of 22.3% by weight per repeating unit.
Synthesis of polyimide precursor (Polymer A-11):
93.7g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride as an acid component was charged into a 1 liter-capacity separable flask, 175g of gamma-butyrolactone was charged, a separately prepared gamma-butyrolactone solution prepared by dissolving 4.7g of 2-isocyanatoethyl methacrylate and 28.9g of pyridine in 20g of gamma-butyrolactone was added thereto for 5 minutes while stirring at room temperature, the mixture was heated at 50℃for 1 hour, 48.7g of 2-hydroxyethyl methacrylate (HEMA) was then charged, and the mixture was heated at 50℃for 4 hours, and the mixture was naturally cooled to room temperature after the completion of the heat release by the reaction. And standing still for 16 hours to obtain a reaction mixture.
Then, a solution obtained by dissolving 69.5g of Dicyclohexylcarbodiimide (DCC) in 70g of gamma-butyrolactone was added to the reaction mixture with stirring under ice cooling for 40 minutes. Then, a solution prepared by dissolving 110g of gamma-butyrolactone in 34.0g of m-TB34.0g as a diamine component was added thereto for 60 minutes while stirring. After stirring at room temperature for 2.5 hours, 15g of ethanol was added, and 150g of gamma-butyrolactone was added after stirring for 30 minutes. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 2700g of ethanol to produce a precipitate containing a crude polymer. The crude polymer thus formed was filtered off and dissolved in 1000g of gamma-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was treated with anion exchange resin (ORGANO CORPORATION "cover) TM 15 ") to give a polymer solution. The resulting polymer solution was added dropwise to 8000g of water to precipitate a polymer, thereby obtainingAfter filtering out the precipitate of (2) and vacuum drying, thereby obtaining polymer A-11 as a powder. The weight average molecular weight (Mw) of this polymer A-11 was measured, and as a result, it was 22,000, the imide group concentration U per repeating unit was 20.1% by weight, and the aliphatic hydrocarbon group concentration T was 8.6% by weight.
(A) Synthesis of polyimide precursor (Polymer A-12):
to a 1 liter-capacity separable flask, 93.7g of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride as an acid component was charged 48.7g of 2-hydroxyethyl methacrylate (HEMA) and 175g of gamma-butyrolactone, and 28.5g of pyridine was added while stirring at room temperature, and the mixture was heated at 50℃for 4 hours, and after completion of the heat release by the reaction, the mixture was cooled to room temperature. And standing still for 16 hours to obtain a reaction mixture.
Then, 4.7g of 2-isocyanatoethyl methacrylate and 0.4g of pyridine were dissolved in 20g of gamma-butyrolactone, and the gamma-butyrolactone solution was added thereto with stirring for 5 minutes, heated at 50℃for 7 hours, and after completion of the heat release by the reaction, cooled naturally to room temperature. And standing still for 16 hours to obtain a reaction mixture.
Then, a solution obtained by dissolving 69.5g of Dicyclohexylcarbodiimide (DCC) in 70g of gamma-butyrolactone was added to the reaction mixture with stirring under ice cooling for 40 minutes. Then, a solution prepared by dissolving 34.0g of 2,2 '-dimethylbiphenyl-4, 4' -diamine (m-TB) as a diamine component in 110g of gamma-butyrolactone was added thereto for 60 minutes while stirring. After stirring at room temperature for 2.5 hours, 15g of ethanol was added, and 150g of gamma-butyrolactone was added after stirring for 30 minutes. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 2700g of ethanol to produce a precipitate containing a crude polymer. The crude polymer thus formed was filtered off and dissolved in 1000g of gamma-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was treated with anion exchange resin (ORGANO CORPORATION "cover) TM 15 ") to give a polymer solution. The resulting polymer solution was added dropwise to 8000g of water to precipitate a polymer, and the precipitate was filtered off and dried under vacuumThus, polymer A-12 was obtained in the form of powder. The weight average molecular weight (Mw) of this polymer A-12 was measured, and as a result, it was 15,000, the imide group concentration U per repeating unit was 20.1% by weight, and the aliphatic hydrocarbon group concentration T was 8.6% by weight.
Synthesis of polyimide precursor (Polymer A-13):
in the synthesis of the above-mentioned polymer A-1, a reaction was carried out in the same manner as described in the synthesis of the polymer A-1 except that in place of the ODPA155.1g, BPDA147.1g was used and in place of the 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane, 85.8g of diaminodiphenyl ether was used, whereby polymer A-13 was obtained. The weight average molecular weight (Mw) of this polymer A-13 was measured, and found to be 22,000. The polyimide obtained from the polymer A-13 had an imide group concentration U of 30.5% by weight and an aliphatic hydrocarbon group concentration T of 0% by weight per repeating unit.
Synthesis of polyimide precursor (Polymer A-14):
polymer A-14 was obtained by performing the reaction in the same manner as described in the synthesis of Polymer A-1 except that 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane was used instead of 191.87g of m-TB92.88 g. The weight average molecular weight (Mw) of this polymer A-14 was measured and found to be 19,000. The polyimide obtained from the polymer A-14 had an imide group concentration U of 28.8% by weight and an aliphatic hydrocarbon group concentration T of 6.2% by weight per repeating unit.
Synthesis of polyimide precursor (Polymer A-15):
polymer A-15 was obtained by performing the reaction in the same manner as described in the synthesis of Polymer A-1 except that 179.59g of 2, 2-bis {4- (4-aminophenoxy) phenyl } propane was used instead of 191.87g of 2, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane in the synthesis of Polymer A-1. The weight average molecular weight (Mw) of this polymer A-15 was measured, and found to be 22,000. The polyimide obtained from the polymer A-15 had an imide group concentration U of 20.5% by weight and an aliphatic hydrocarbon group concentration T of 4.4% by weight per repeating unit.
Synthesis of polyimide precursor (Polymer A-16):
in the synthesis of the above polymer A-1, 309.29g of 2,2', 3', 5' -hexamethyl [1,1' -biphenyl ] -4,4' -diyl=bis (1, 3-dioxo-1, 3-dihydro-2-benzofuran-5-carboxylate) (Bis (1, 3-dioxo-1, 3-dihydrobenzofuran5-carboxilic acid) 2,2', 3', 5' -hexamethylbip henyl-4,4' -diyl ester) was used instead of ODPA155.1g, and 179.59g of 2, 2-Bis {4- (4-aminophenoxy) phenyl } propane was used instead of 191.87g of 2, 2-Bis [4- (4-aminophenoxy) -3-methylphenyl ] propane, and the reaction was carried out in the same manner as described in the synthesis of the polymer A-1, to obtain the polymer A-16. The weight average molecular weight (Mw) of this polymer A-16 was measured, and found to be 29,000. The polyimide obtained from the polymer A-16 had an imide group concentration U of 14.1% by weight and an aliphatic hydrocarbon group concentration T of 12.1% by weight.
[ production of photosensitive resin composition ]
The following compounds were used in examples and comparative examples.
Photopolymerization initiator B-1: TR-PBG-304 (manufactured by Changzhou Strong electronic Co., ltd.)
Photopolymerization initiator B-2: TR-PBG-305 (manufactured by Changzhou Strong electronic Co., ltd.)
Photopolymerization initiator B-3: TR-PBG-3057 (manufactured by Changzhou Strong electronic Co., ltd.)
C-1: gamma-butyrolactone (GBL)
C-2: dimethyl sulfoxide (DMSO)
D-1: 3-epoxypropoxypropyl trimethoxysilane (Xinyue chemical Co., ltd.)
D-2: n-phenyl-3-aminopropyl trimethoxysilane (manufactured by Xinyue chemical Co., ltd.)
D-3: (3-Triethoxysilylpropyl) -tert-butylcarbamate
D-4: ureidopropyltriethoxysilane (Xinyue chemical Co., ltd.)
E-1:1, 9-nonanediol dimethacrylate (New Zhongcun chemical Co., ltd.)
E-2:1, 6-hexanediol dimethacrylate (New Zhongcun chemical Co., ltd.)
E-3: diacrylate of polyoxypropylene bisphenol A (manufactured by Kyowa Kagaku Co., ltd.)
F-1: BMI-5100 (manufactured by Dahe chemical industry Co., ltd.)
F-2: SBB70P (manufactured by Xuhua chemical Co., ltd.)
G-1: k180SP-CY1 (manufactured by Admatechs Co., ltd.)
Example 1 >
As shown in table 1, a negative photosensitive resin composition was prepared using the polyimide precursor a-1 by the following method, and the prepared composition was evaluated. A-1 to be a polyimide precursor of (a): 100g of B-1 as (B) photopolymerization initiator: 5g of GBL dissolved in the solvent of (C): 180g, DMSO:20 g. The viscosity of the resulting solution was further adjusted to about 40 poise by adding a small amount of GBL, and the resulting solution was used as a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in table 2 below.
Examples 2 to 26 and comparative examples 1 to 3 >, respectively
Negative photosensitive resin compositions similar to those in example 1 were prepared in accordance with the compounding ratios shown in tables 1, 3 and 5 below, and the same evaluation as in example 1 was performed. The results are shown in tables 2, 4 and 6 below.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
As shown in tables 1 to 6, the dielectric loss tangent (Df) at 40GHz of the photosensitive resin compositions of examples 1 to 27 showed values as low as 0.0059 to 0.012, compared to comparative examples 1 to 3. In the case of the photosensitive resin compositions of examples 1 to 27, the product of the moisture permeability and the dielectric loss tangent was 3.91 to 9.41, which is lower than that of the comparative example. The development time was long for comparative examples 1 and 2, and the resolution of comparative example 1 was "D".
Industrial applicability
By using the photosensitive resin composition of the present invention, a cured film having high resolution and low dielectric loss tangent can be obtained when the film is thick. Therefore, the photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for manufacturing electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (19)

1. A photosensitive resin composition comprising:
(A) 100 parts by mass of at least one resin selected from polyimide and polyimide precursor;
(B) 0.5 to 10 parts by mass of a sensitizer; and
(C) 100-300 parts by mass of a solvent;
in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃, the concentration U of imide groups is 12-26 wt%, the concentration U of imide groups is the proportion of the molecular weight of imide groups relative to the molecular weight of repeating units containing a structure from tetracarboxylic dianhydride and diamine,
the resin comprises a structure represented by the following general formula (14),
in the formula (14), R 15 Is an organic group with 1-5 carbon atoms, R 16 、R 17 R is R 18 Each independently is a single bond optionally forming a ring structure or an alkyl group optionally forming a ring structure having 1 to 10 carbon atoms, or an organic group containing an aromatic ring having 6 to 10 carbon atoms, m 9 Is an integer selected from 1 to 4, m 10 、m 11 M 12 Each independently is an integer selected from 0 to 4, Z 2 Is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and represents a linking portion with the main chain of the resin.
2. The photosensitive resin composition according to claim 1, wherein the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃ has an aliphatic hydrocarbon group concentration of 4 to 35wt%, and the aliphatic hydrocarbon group concentration is a ratio of the total of the molecular weights of the aliphatic hydrocarbon groups to the molecular weight of the repeating unit including the structure derived from the tetracarboxylic dianhydride and the diamine compound.
3. The photosensitive resin composition according to claim 1 or 2, wherein the structure represented by the general formula (14) is derived from a diamine.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the resin is a polyimide precursor.
5. The photosensitive resin composition according to claim 4, wherein the polyimide precursor comprises a structure represented by the following general formula (4),
in the formula (4), X 1 Is a C6-40 organic group of 4 valence, Y 1 An organic group having a valence of 2 and having 6 to 40, n 1 R is an integer of 2 to 150 4 And R is 5 Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 40 carbon atoms, wherein R 4 And R is 5 At least one of them is a group represented by the following general formula (5),
in the formula (5), R 6 、R 7 And R is 8 Each independently is a hydrogen atom or a 1-valent organic group having 1 to 3 carbon atoms, and m 2 Is an integer of 2 to 10.
6. A photosensitive resin composition comprising:
(A) 100 parts by mass of at least one resin selected from polyimide and polyimide precursor;
(B) 0.5 to 10 parts by mass of a sensitizer; and
(C) 100-300 parts by mass of a solvent;
when the resin contains a polyimide precursor, the polyimide precursor is represented by the following general formula (4),
In the formula (4), X 1 Is a C6-40 organic group of 4 valence, Y 1 An organic group having a valence of 2 and having 6 to 40, n 1 R is an integer of 2 to 150 4 And R is 5 Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 40 carbon atoms, wherein R 4 And R is 5 At least one of them is a group represented by the following general formula (5),
in the formula (5), R 6 、R 7 And R is 8 Each independently is a hydrogen atom or a 1-valent organic group having 1 to 3 carbon atoms, and m 2 Is an integer of 2 to 10, and is a compound,
the resin comprises a structure represented by the following general formula (15),
in the formula (15), rz each independently represents a 1-valent organic group having 1 to 10 carbon atoms optionally containing a halogen atom and optionally forming a cyclic structure, a represents an integer of 0 to 4, a is each independently an oxygen atom or a sulfur atom, and B is 1 of the following formulas:
the resin comprises a structure represented by the following general formula (14),
in the formula (14), R 15 Is an organic group with 1-5 carbon atoms, R 16 、R 17 R is R 18 Each independently is a single bond optionally forming a ring structure or an alkyl group optionally forming a ring structure having 1 to 10 carbon atoms, or an organic group containing an aromatic ring having 6 to 10 carbon atoms, m 9 Is an integer selected from 1 to 4, m 10 、m 11 M 12 Each independently is an integer selected from 0 to 4, Z 2 Is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and represents a linking portion with the main chain of the resin.
7. A photosensitive resin composition comprising:
(A) 100 parts by mass of at least one resin selected from polyimide and polyimide precursor;
(B) 0.5 to 10 parts by mass of a sensitizer; and
(C) 100-300 parts by mass of a solvent;
in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ℃, the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic dianhydride and the diamine is set to be the imide group concentration U, and the ratio of the total molecular weight of the aliphatic hydrocarbon groups to be the aliphatic hydrocarbon group concentration T, X is 12 to 26wt%, and the following formula (1) is satisfied:
-12.6＜U-T＜16.0(1){。
8. a photosensitive resin composition comprising:
(A) 100 parts by mass of at least one resin selected from polyimide and polyimide precursor;
(B) 0.5 to 10 parts by mass of a sensitizer; and
(C) 100-300 parts by mass of a solvent;
in the IR spectrum of a polyimide obtained by heating and curing the polyimide precursor (A) at 230 ℃, the polyimide precursor (A) was brought to 1450cm -1 1550cm above -1 The maximum peak intensity among the absorption peaks in the following range was set to Ph 1 Setting the second highest peak intensity to Ph 2 Will 1380cm -1 The peak intensity in the vicinity is set to Im 1 And set Ph 1 When normalized for 1, the following formula (2) is satisfied:
0.34≤Ph 2 ×Im 1 ≤1.2 (2)。
9. the photosensitive resin composition according to any one of claims 1 to 8, wherein the resin is a reaction product of tetracarboxylic dianhydride and diamine.
10. The photosensitive resin composition according to claim 9, wherein at least one of the tetracarboxylic dianhydrides and at least one of the diamines constituting the resin have an aliphatic hydrocarbon group.
11. The photosensitive resin composition according to any one of claims 1 to 10, further comprising (D) a silane coupling agent.
12. The photosensitive resin composition according to any one of claims 1 to 11, further comprising (E) a radical polymerizable compound.
13. The photosensitive resin composition of claim 12, wherein (E) the radical polymerizable compound has an alkyl group.
14. The photosensitive resin composition according to any one of claims 1 to 13, further comprising (F) a thermal crosslinking agent.
15. The photosensitive resin composition according to any one of claims 1 to 14, further comprising (G) a filler.
16. A method for producing a polyimide cured film, comprising the steps of:
A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of claims 1 to 15 to the substrate;
a step of heating and drying the photosensitive resin layer obtained;
exposing the heated and dried photosensitive resin layer to light;
developing the photosensitive resin layer after exposure; and
and a step of forming a polyimide cured film by heat-treating the developed photosensitive resin layer.
17. The method for producing a cured polyimide film according to claim 16, wherein the coating and developing steps are performed so as to obtain a photosensitive resin layer having a thickness of 10 μm to 15 μm in the developing step, and a developing time during development is 30 seconds or less.
18. A polyimide cured film having a dielectric loss tangent of 0.003 to 0.014 at a frequency of 40GHz by a perturbed split cylindrical resonator method and satisfying the following formula (3):
3＜tanδ 40 ×WVTR＜10 (3)
in formula (3), tan delta 40 The dielectric loss tangent at 40GHz, which is a frequency based on the perturbed split-cylinder resonator method, is shown, and WVTR shows the moisture permeability of the cured polyimide film converted to a film thickness of 10. Mu.m.
19. The photosensitive resin composition according to any one of claims 1 to 15, wherein the photosensitive resin composition is used for rewiring layer use.
CN202280011177.4A 2021-01-22 2022-01-12 Photosensitive resin composition, method for producing polyimide cured film using same, and polyimide cured film Pending CN116802560A (en)

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