CN108700805B - Photosensitive resin composition, dry film, cured product, printed wiring board, and photobase generator - Google Patents

Photosensitive resin composition, dry film, cured product, printed wiring board, and photobase generator Download PDF

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CN108700805B
CN108700805B CN201780011878.7A CN201780011878A CN108700805B CN 108700805 B CN108700805 B CN 108700805B CN 201780011878 A CN201780011878 A CN 201780011878A CN 108700805 B CN108700805 B CN 108700805B
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resin composition
photosensitive resin
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photobase generator
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CN108700805A (en
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郭扬眉
三轮崇夫
有光晃二
冈安克起
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Taiyo Holdings Co Ltd
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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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/56—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups bound to carbon atoms of six-membered aromatic rings and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

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  • Materials For Photolithography (AREA)
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  • Polyurethanes Or Polyureas (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

Providing: a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, a printed wiring board having the cured product, and a photobase generator having excellent sensitivity. A photosensitive resin composition, and the like, the photosensitive resin composition being characterized by containing: an ionic photobase generator comprising a carboxylic acid represented by the following general formula (1) and a base. (in the formula (1), R 1 ～R 4 、X 1 And X 2 Each independently being a hydrogen atom or a substituent, X 1 And X 2 At least one of them is an electron-withdrawing group, Y is an electron-donating group, and B represents a base. ).

Description

Photosensitive resin composition, dry film, cured product, printed wiring board, and photobase generator
Technical Field
The invention relates to a photosensitive resin composition, a dry film, a cured product, a printed circuit board and a photobase generator.
Background
A method of chemically modifying a resin using a photobase generator that generates a base due to the action of light as a catalyst is applied to the fields of photoresist materials, photocurable materials, and the like. For example, patent document 1 describes a photosensitive resin composition containing: a photobase generator comprising a salt of a carboxylic acid which undergoes decarboxylation with a tertiary amine; and, a polyimide precursor and/or a polybenzoxazole precursor.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4830435
Disclosure of Invention
Problems to be solved by the invention
It is required to improve the sensitivity of a photosensitive resin composition containing a photobase generator. If the sensitivity is improved, reaction conditions such as conditions for light irradiation for generating alkali and conditions for heat treatment in thermosetting with alkali can be alleviated, and patterning with good resolution is also expected. Further, if the sensitivity is improved, the range of selection of the reaction conditions as described above is widened, and it is expected that reaction conditions more suitable than the conventional one can be selected in consideration of characteristics such as heat resistance of other components in the photosensitive resin composition and other materials such as a base material to which the photosensitive resin composition is applied. However, the photobase generator described in patent document 1, which contains a salt of a carboxylic acid and a tertiary amine that undergo a decarboxylation, cannot achieve sufficient sensitivity.
Accordingly, an object of the present invention is to provide: a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, a printed wiring board having the cured product, and a photobase generator having excellent sensitivity.
Means for solving the problems
The present inventors have conducted extensive studies in view of the above, and as a result, have found that: the above problems can be solved by using a compound having a specific structure as a photobase generator, and the present invention has been completed.
That is, the photosensitive resin composition of the present invention is characterized by containing: an ionic photobase generator comprising a carboxylic acid represented by the following general formula (1) and a base.
Figure BDA0001767876040000021
(in the formula (1), R 1 ～R 4 、X 1 And X 2 Each independently being a hydrogen atom or a substituent, X 1 And X 2 At least one of them is an electron withdrawing group, Y is an electron donating group, and B represents a base. )
In the photosensitive resin composition of the present invention, the photobase generator preferably has a molar absorptivity of 300L & mol -1 ·cm -1 The above.
In the photosensitive resin composition of the present invention, it is preferable that in the general formula (1), the electron-withdrawing group is selected from the group consisting of-C.ident.N and-NO 2 、-COCH 3 -F, -Cl, -Br and-I.
In the photosensitive resin composition of the present invention, it is preferable that in the general formula (1), the electron-donating group is selected from the group consisting of-CH 3 、-C 2 H 5 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-C 6 H 5 、-OH、-OCH 3 and-OC 6 H 5 Group (d) of (a).
The photosensitive resin composition of the present invention preferably further contains a polymer precursor.
In the photosensitive resin composition of the present invention, the polymer precursor is preferably at least one of polyamic acid and polyamic acid ester.
In the photosensitive resin composition of the present invention, the polymer precursor is preferably a polyamic acid ester having a structure represented by the following general formula (4-1).
Figure BDA0001767876040000031
(in the formula (4-1), R 7 Is a 4-valent organic radical, R 8 R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group 9-1 And R 10-1 Optionally identical to or different from one another, are organic radicals having a valence of 1 or functional groups having silicon, R 11 Is a 2-valent organic group, m is an integer of 1 or more, and n is an integer of 0 or 1 or more. )
In the photosensitive resin composition of the present invention, R in the general formula (4-1) 7 Is a 4-valent organic group containing a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, a 4-valent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a 4-valent organic group containing a fluorine atom.
In the photosensitive resin composition of the present invention, the polymer precursor is preferably a polyamic acid ester having a structure represented by at least one of the following general formulae (4-1-1) and (4-1-2).
Figure BDA0001767876040000032
(in the formula (4-1-1), R 8 R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group 9-1 And R 10-1 Optionally identical to or different from one another, are organic radicals having a valence of 1 or functional groups having silicon, R 11 Is a 2-valent organic group, m is an integer of 1 or more, and n is an integer of 0 or 1 or more. )
Figure BDA0001767876040000033
(in the formula (4-1-2), R 8 Is a group having an alicyclic skeleton, a phenylene group, a diphenylene group having alkylene bondsAny of the group of the basic skeleton and alkylene, R 9-1 And R 10-1 Optionally identical to or different from one another, are organic radicals having a valence of 1 or functional groups having silicon, R 11 Is a 2-valent organic group, m is an integer of 1 or more, and n is an integer of 0 or 1 or more. )
The dry film of the present invention is characterized by comprising a resin layer obtained by applying the photosensitive resin composition to a film and drying the film.
The cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of the dry film.
The printed wiring board of the present invention is characterized by having the cured product.
The photobase generator of the present invention is characterized by being an ionic type formed by a carboxylic acid represented by the following general formula (1) and a base.
Figure BDA0001767876040000041
(in the formula (1), R 1 ～R 4 、X 1 And X 2 Each independently being a hydrogen atom or a substituent, X 1 And X 2 At least one of them is an electron-withdrawing group, Y is an electron-donating group, and B represents a base. )
In the photobase generator of the present invention, it is preferable that in the general formula (1), the electron-withdrawing group is-C.ident.N, -COCH 3 、-NO 2 -F, -Cl, -Br and-I.
In the photobase generator of the present invention, it is preferable that in the general formula (1), the electron donating group is-CH 3 、-C 2 H 5 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-C 6 H 5 、-OH、-OCH 3 and-OC 6 H 5 。
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a photosensitive resin composition having excellent sensitivity, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, a printed wiring board having the cured product, and a photobase generator having excellent sensitivity.
Drawings
FIG. 1 is a diagram showing the photobase generator MONPA-TBD synthesized in example 1-1 1 Graph of H-NMR spectrum. The horizontal axis represents chemical shift (. delta.) and the vertical axis represents relative intensity (ppm).
FIG. 2 is a diagram showing photobase generator MONPA-DBU synthesized in example 1-2 1 Graph of H-NMR spectrum. The horizontal axis represents chemical shift (. delta.) and the vertical axis represents relative intensity (ppm).
FIG. 3 is a diagram showing photobase generator MONPA-2E4MZ synthesized in examples 1-3 1 Graph of H-NMR spectrum. The horizontal axis represents chemical shift (. delta.) and the vertical axis represents relative intensity (. ppm).
FIG. 4 is a diagram showing photobase generators MONPA-DBA synthesized in examples 1 to 4 1 Graph of H-NMR spectrum. The horizontal axis represents chemical shift (. delta.) and the vertical axis represents relative intensity (ppm).
Detailed Description
The components contained in the photosensitive resin composition of the present invention will be described in detail below.
[ photobase generators ]
In the present invention, an ionic photobase generator comprising a carboxylic acid represented by the following general formula (1) and a base is used.
Figure BDA0001767876040000051
(in the formula (1), R 1 ～R 4 、X 1 And X 2 Each independently being a hydrogen atom or a substituent, X 1 And X 2 At least one of them is an electron withdrawing group, Y is an electron donating group, and B represents a base. Here, the substituent means a group other than a hydrogen atom. )
The photobase generator has a structure in which an electron-withdrawing group and an electron-donating group are directly bonded to the meta-position and the para-position of a benzene ring derived from phenylacetic acid, respectively. With such a structure, a base can be generated.
In addition, with the structure, the device canA photobase generator having high sensitivity even to i-rays (365nm) can be produced. The photobase generator preferably has a molar absorptivity at i-ray of 300 L.mol -1 ·cm -1 More preferably 500 L.mol or more -1 ·cm -1 More preferably 1100 L.mol or more -1 ·cm -1 The above. The higher the molar absorption coefficient, the higher the sensitivity tends to be. The upper limit of the molar absorption coefficient is not particularly limited, and is, for example, 20000 L.mol from the viewpoint of photostability and storage stability -1 ·cm -1 The following.
Further, since the photobase generator has a high pyrolysis temperature (Td), it is excellent in thermal stability when a coating film is dried, for example. The Td of the photobase generator is preferably 120 ℃ or higher, more preferably 150 ℃ or higher, and most preferably 180 ℃ or higher. The pyrolysis temperature (Td) is a temperature at which the weight loss ratio becomes 10%.
The active light for the photobase generator may be visible light, ultraviolet light, electron beam, X-ray, or the like, and ultraviolet light, particularly ultraviolet light of 248nm, 365nm, 405nm, or 436nm, is preferable.
In the above general formula (1), R 1 、R 2 、X 1 And X 2 Each independently a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silyl group, a silanol group, a cyano group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphate group, a phosphono group, a phosphonate group, an alkoxy group, an amide group, and an organic group.
Here, the organic group means a group containing a carbon atom, and may have an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, or the like)) such as a group having 10 or less carbon atoms.
X 1 And X 2 The electron-withdrawing group that can be used is not particularly limited, and examples thereof include-C.ident.N and-COCH 3 、-NO 2 And halogen atoms such as-F, -Cl, -Br, -I. Among the electron-withdrawing groups, -NO is preferred 2 . To be explainedIs, X 1 And X 2 When only one of them is an electron-withdrawing group, the other is not particularly limited.
The electron-donating group that can be used for Y is not particularly limited, and examples thereof include-CH 3 、-C 2 H 5 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-C 6 H 5 、-OH、-OCH 3 and-OC 6 H 5 . Among them, the-OCH group is preferable 3 。
R 1 And R 2 The substituent which can be used is not particularly limited, and examples thereof include an electron-donating group. R 1 And R 2 Preferably each hydrogen atom.
R 3 And R 4 The substituent which may be used is not particularly limited, and may be the same or different, and is, for example, a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silyl group, a silanol group, a cyano group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or an organic group. R is 3 And R 4 Preferably each hydrogen atom.
In addition, R is 1 、R 2 、X 1 、X 2 And Y preferably does not form a cyclic structure.
The base represented by B is not particularly limited, and examples thereof include amines (amine compounds) such as primary amines, secondary amines, and tertiary amines, nitrogen-containing cyclic compounds such as pyridine, hydrazine compounds, amide compounds, and quaternary ammonium hydroxides. In addition, for example, a base such as an amine disclosed in international publication No. WO2009/19979 may be used. Among the bases, secondary amines, tertiary amines, and nitrogen-containing cyclic compounds are preferable. The base shown in B is preferably a strong base.
Examples of the base include: examples of the compound include 1, 4-diazabicyclo [2.2.2] octane (DABCO), N-dimethyl-4-aminopyridine (DMAP), 1-azabicyclo [2.2.2] octane (ABCO), 1, 8-bis (dimethylamino) naphthalene (DMAN), Diazabicycloundecene (DBU), Diazabicyclononene (DBN), 1,3, 3-Tetramethylguanidine (TMG), 2-ethyl-4-methylimidazole (2E4MZ), piperidine (PPD), 1-ethyl-piperidine (EPPD), Dibutylamine (DBA), and 1,5, 7-triazabicyclo [4.4.0] -5-decene (TBD).
Figure BDA0001767876040000071
The pKa of the base is preferably 8 to 20, more preferably 10 to 16.
The aforementioned base is preferably DMAP, DMAN, DBU, TMG, 2E4MZ, PPD, EPPD, DBA and TBD.
The photobase generator is preferably a photobase generator represented by the following general formula (2).
Figure BDA0001767876040000072
In the formula (2), X 1 、X 2 Y and B are the same as those in the formula (1).
The photobase generator is more preferably a photobase generator represented by the following general formula (3).
Figure BDA0001767876040000081
In formula (3), B is the same as in formula (1).
Hereinafter, specific examples of the photobase generator include, but are not limited to, photobase generators prepared from 4-methoxy-3-nitrophenylacetic acid (MONPA) and various bases.
Figure BDA0001767876040000082
The photobase generator may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The amount of the photobase generator is preferably 3 to 50% by mass, more preferably 10 to 30% by mass based on the total amount of the photosensitive resin composition.
The photosensitive resin composition of the present invention may contain a photobase generator other than the photobase generator described above within a range not to impair the effects of the present invention.
(Polymer precursor)
The photosensitive resin composition of the present invention may contain a polymer precursor as a resin component modified with a base generated from the photobase generator as a catalyst. The polymer precursor may be, for example, a polyimide precursor having a repeating unit of polyamic acid or polyamic acid ester.
The polymer precursor having a repeating unit of polyamic acid or polyamic acid ester is preferably represented by the following general formula (4).
Figure BDA0001767876040000091
In the formula (4), R 7 Is a 4-valent organic radical, R 8 Is an organic radical having a valence of 2, R 11 Is an organic group having a valence of 2. As R 11 Examples thereof include: and groups containing, as a constituent component, a phenol group, an alkylphenol group, a (meth) acrylate group, a cyclic alkyl group, a cyclic alkenyl group, a hydroxyamididoyl group, an aromatic or aliphatic ester group, an amide imide group, a carbonate group, a siloxane group, an alkylene oxide, a urethane group, an epoxy group, an oxetane group, and the like. Here, the organic group means a group containing a carbon atom.
m is an integer of 1 or more, and n is 0 or an integer of 1 or more. Here, the number average molecular weight of the polymer precursor is preferably 1000 to 100 ten thousand, more preferably 5000 to 50 ten thousand, and further preferably 1 ten thousand to 20 ten thousand.
In the formula (4), R 7 And R 8 The aromatic group is selected according to the application, preferably an aromatic group with 6-32 carbon atoms, or an aliphatic group, preferably an aliphatic group with 4-20 carbon atoms. R 7 And R 8 Preferably, the substituent R contained in the acid dianhydride and diamine described later used for producing the polymer precursor 7 And R 8 。
In addition, when the photosensitive resin composition is patterned by short-wavelength light, R is the number R from the viewpoint of absorption characteristics of the polymer 7 And R 8 Preferably, aliphatic groups are used. In addition, for example, a fluorine-containing group is usedGroup as R 7 And R 8 In the case of (3), the wavelength reduction of light absorption and the dielectric characteristics can be improved.
In the present invention, it is important to select the structure of the polymer precursor depending on the application.
In addition, R is 7 The valence of (4) represents the valence only for bonding with an acid, R 7 May have a substituent. Likewise, R 8 The 2-valent radical of (2) represents a valence number for bonding to an amine only, and may further have a substituent.
R 9 And R 10 Is a hydrogen atom or a 1-valent organic group or a functional group having silicon.
R 9 And R 10 Examples of the organic group having a valence of 1 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. R 9 And R 10 Examples of the functional group having silicon having a valence of 1 include a siloxane group, a silane group, and a silanol group. And R may also be 9 And R 10 Only a part is hydrogen or a monovalent organic group, and thus, the solubility can be controlled.
As the polymer precursor, R is suitably used 9 And R 10 A polyamic acid such as a hydrogen atom. This improves the alkali developability and enables formation of a favorable pattern.
(Polyamic acid)
The polyamic acid can be prepared by applying a conventionally known method. For example, it can be prepared by merely mixing an acid dianhydride and a diamine in a solution. Can be synthesized in 1-step reaction, can be obtained easily at low cost, and does not require further modification, and therefore, it is preferably used. The method for synthesizing the polymer precursor is not particularly limited, and a known method can be applied.
Examples of the tetracarboxylic dianhydride which can be used in the present invention include those represented by the following general formula (5). However, the specific examples shown below are examples, and it is needless to say that known substances can be used as long as the gist of the present invention is not impaired.
Figure BDA0001767876040000101
(R in the formula 7 As indicated above. )
In addition, R in the repeating unit in the polyamic acid of the present embodiment 7 The radical is preferably R derived from tetracarboxylic dianhydride used as a raw material for producing polyamic acid 7 。
Examples of the acid dianhydride which can be used for producing the polymer precursor include: aliphatic tetracarboxylic acid dianhydrides such as 1,3,3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-c ] furan-1, 3-dione, ethylenetetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, methylcyclobutanetetracarboxylic acid dianhydride, and cyclopentanetetracarboxylic acid dianhydride; pyromellitic dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 2,3 ', 3, 4' -benzophenonetetracarboxylic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic dianhydride, 2,3 ', 3, 4' -biphenyltetracarboxylic dianhydride, 2 ', 6, 6' -biphenyltetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, 2-bis (3, 4-dicarboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane dianhydride, 2-bis (2, 3-dicarboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane dianhydride, 1, 3-bis [ (3, 4-dicarboxy) benzoyl ] benzene dianhydride, 1, 4-bis [ (3, 4-dicarboxy) benzoyl ] benzene dianhydride, 2-bis {4- [ 4- (1, 2-dicarboxy) phenoxy ] phenyl } propane dianhydride, 2-bis {4- [3- (1, 2-dicarboxy) phenoxy ] phenyl } propane dianhydride, Bis {4- [ 4- (1, 2-dicarboxy) phenoxy ] phenyl } ketone dianhydride, bis {4- [3- (1, 2-dicarboxy) phenoxy ] phenyl } ketone dianhydride, 4 '-bis [ 4- (1, 2-dicarboxy) phenoxy ] biphenyl dianhydride, 4' -bis [3- (1, 2-dicarboxy) phenoxy ] biphenyl dianhydride, bis {4- [ 4- (1, 2-dicarboxy) phenoxy ] phenyl } ketone dianhydride, bis {4- [3- (1, 2-dicarboxy) phenoxy ] phenyl } ketone dianhydride, bis {4- [ 4- (1, 2-dicarboxy) phenoxy ] phenyl } sulfone dianhydride, bis {4- [3- (1, 2-dicarboxy) phenoxy ] phenyl } sulfone dianhydride, Bis {4- [ 4- (1, 2-dicarboxy) phenoxy ] phenyl } sulfide dianhydride, bis {4- [3- (1, 2-dicarboxy) phenoxy ] phenyl } sulfide dianhydride, 2-bis {4- [ 4- (1, 2-dicarboxy) phenoxy ] phenyl } -1,1,1,3,3, 3-hexafluoropropane dianhydride, 2-bis {4- [3- (1, 2-dicarboxy) phenoxy ] phenyl } -1,1,1,3,3, 3-hexafluoropropane dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (2, 3-or 3, 4-dicarboxyphenyl) propane dianhydride, 1,4, aromatic tetracarboxylic acid dianhydrides such as 5, 8-naphthalenetetracarboxylic acid dianhydride, 1,2,5, 6-naphthalenetetracarboxylic acid dianhydride, 1,2,3, 4-benzenetetracarboxylic acid dianhydride, 3,4,9, 10-perylenetetracarboxylic acid dianhydride, 2,3,6, 7-anthracenetetracarboxylic acid dianhydride, 1,2,7, 8-phenanthrenetetracarboxylic acid dianhydride, pyridinetetracarboxylic acid dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3, 3 ', 4, 4' -tetracarboxylic acid dianhydride, and p-terphenyl-3, 3 ', 4, 4' -tetracarboxylic acid dianhydride.
These may be used alone or in combination of 2 or more. Further, as the tetracarboxylic dianhydride which is particularly preferably used, 1,3,3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-c ] furan-1, 3-dione, pyromellitic dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 2 ', 6, 6' -biphenyltetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 2-bis (3, 4-dicarboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane dianhydride may be mentioned.
When acid dianhydride containing fluorine and acid dianhydride having an alicyclic skeleton are used in combination, physical properties such as solubility and thermal expansion coefficient can be adjusted without significantly deteriorating transparency. Further, when a rigid acid dianhydride such as pyromellitic anhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, or 1,4,5, 8-naphthalenetetracarboxylic dianhydride is used, the linear thermal expansion coefficient of the finally obtained polyimide tends to be small, but the improvement of transparency tends to be inhibited, and therefore, the polyimide can be used in combination while paying attention to the copolymerization ratio.
The acid dianhydride may have a plurality of carboxyl groups on a single aromatic ring or a plurality of aromatic rings, and for example, an acid dianhydride represented by the following formula may be used.
Figure BDA0001767876040000121
Examples of the amine that can be used in the present invention include diamines represented by the following general formula (6). However, the following is an example, and it is needless to say that a known diamine can be used without departing from the gist of the present invention.
H 2 N-R 8 -NH 2 (6)
(R in the formula 8 As indicated above. )
As R 8 Examples of the diamine in the case where the group is an aromatic group having a valence of 2 include p-phenylenediamine, 3 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dichloro-4, 4' -diaminobiphenyl, 9, 10-bis (4-aminophenyl) anthracene, 4 '-diaminobenzophenone, 4' -diaminodiphenyl sulfone, 3 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfoxide, 1, 3-bis (3-aminophenoxy) benzene, bis [ 4- (4-aminophenoxy) phenyl ] sulfone, bis [ 4- (3-aminophenoxy) phenyl ] sulfone, and the like, 4,4 ' -bis (4-aminophenoxy) biphenyl, 4 ' -bis (3-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl ] ether, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (4-aminophenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3-amino-4-methylphenyl) propane, m-phenylenediamine, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl sulfide, 3,4 ' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene.
As R 8 Examples of diamines in which the group is a 2-valent aliphatic group include 1, 1-m-xylylenediamine, 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4-diaminoheptamethylenediamine, 1, 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4, 7-methylidene-dimethylenediamine, and tricyclo [6.2.1.02,7 ]]Undecenyldimethyl diamine, 4' -methylenediamineMethyl bis (cyclohexylamine), isophorone diamine.
Further, as another example, there can be mentioned diaminopolysiloxane represented by the following general formula (11) and the like.
Figure BDA0001767876040000131
Wherein, in the formula, R 28 And R 29 Each independently represents a divalent hydrocarbon group, R 30 And R 31 Each independently represents a monovalent hydrocarbon group. p is an integer of 1 or more, preferably 1 to 10.
Specifically, R in the above formula (11) is 28 And R 29 Examples thereof include alkylene groups having 1 to 7 carbon atoms such as methylene, ethylene and propylene, and arylene groups having 6 to 18 carbon atoms such as phenylene, and R is 30 And R 31 Examples thereof include alkyl groups having 1 to 7 carbon atoms such as methyl group and ethyl group, and aryl groups having 6 to 12 carbon atoms such as phenyl group.
As the polymer precursor, a polyamic acid ester can be suitably used. The polyamic acid ester can be obtained by a known method.
For example, an acid anhydride such as 3, 3' -benzophenonetetracarboxylic dianhydride is reacted with an alcohol such as ethanol to form a half ester. The half ester is formed into the diester diacid chloride using thionyl chloride. This diester diacid chloride is reacted with a diamine such as 3, 5-diaminobenzoic acid to obtain a polyamic acid ester.
In the photosensitive resin composition, a single type of material may be used as the polymer precursor having a repeating unit of polyamic acid or polyamic acid ester in at least a part thereof, or a plurality of types of materials may be used as a mixture. In addition, R may be 7 And R 8 A copolymer in which at least any one of the structures is formed of a plurality of structures.
Further, a half ester obtained by reacting the acid anhydride with an alcohol is reacted with a diisocyanate such as isophorone diisocyanate to obtain a polyamic acid ester. In addition, the synthesis method using diisocyanate enables polyamide acid ester to be synthesized more easily than the synthesis method using diamine.
Examples of the diisocyanate that can be used to obtain the polyamic acid ester include diisocyanates represented by the following general formula (7). However, the following is an example, and a known diisocyanate can be used without departing from the gist of the present invention.
OCN-R 8 -NCO (7)
(R in the formula 8 As indicated above. )
Examples of the diisocyanate include isophorone diisocyanate (ITI), Toluene Diisocyanate (TDI), methylene diphenyl 4, 4' -diisocyanate (MDI), 2-bis (4-isocyanatophenyl) hexafluoropropane, and hexamethylene diisocyanate (HMDI).
The polymer precursor is preferably a polyamic acid ester having a structure represented by the following general formula (4-1).
Figure BDA0001767876040000141
(in the formula (4-1), R is the same as in the formula (4) 7 Is a 4-valent organic radical, R 8 Is an organic radical having a valence of 2, R 11 Is a 2-valent organic group, m is an integer of 1 or more, and n is an integer of 0 or 1 or more. R is 9-1 And R 10-1 Optionally identical to or different from each other, are organic groups having a valence of 1 or functional groups having silicon. R 8 Preferably, the group has an alicyclic skeleton, phenylene, a group having a diphenylene skeleton bonded with alkylene, or alkylene. )
In the formula (4-1), R 7 The organic group having a valence of 4 is not particularly limited, and may be selected according to the application. Examples thereof include: an aromatic group, preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, preferably an aliphatic group having 4 to 20 carbon atoms. R 7 Preferably, the substituent R contained in the acid dianhydride represented by the general formula (5) used for producing the polymer precursor 7 。
For the polyamic acid ester having the structure represented by the foregoing general formula (4-1), resolution is obtainedFrom the viewpoint of rate, R 7 Particularly preferred is a 4-valent organic group containing a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, a 4-valent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a 4-valent organic group containing a fluorine atom.
The aforementioned organic group having a valence of 4 and containing a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthyl group, and particularly a phenyl group), preferably has a trifluoromethyl group and an aromatic group.
The polyamic acid ester having a structure represented by the general formula (4-1) preferably has a structure represented by at least one of the following general formulae (4-1-1) and (4-1-2).
Figure BDA0001767876040000151
(in the formula (4-1-1), R 8 、R 9-1 、R 10-1 、R 11 M and n are the same as those in the formula (4-1). )
Figure BDA0001767876040000152
(in the formula (4-1-2), R 8 、R 9-1 、R 10-1 、R 11 M and n are the same as those in the formula (4-1). )
R in the formula (4-1) 8 Preferably, the group has an alicyclic skeleton, phenylene, a group having a diphenylene skeleton bonded with alkylene, or alkylene. The aforementioned phenylene group and alkylene group are each independently substituted with R in the formula (4-1) 8 The 2 nitrogen atoms bonded are directly bonded. On the other hand, the alicyclic skeleton and the alkylene-bonded diphenylene skeleton may be bonded to R in the formula (4-1) 8 The 2 nitrogen atoms bonded are directly bonded or may not be bonded. R 8 Preferably, the substituent R contained in the diamine represented by the general formula (6) or the diisocyanate represented by the general formula (7) used for producing the polymer precursor 8 。
R 8 The group having an alicyclic skeleton in (1) may have a substituent or may have a substituentFused rings may be formed. The group having an alicyclic skeleton is preferably represented by the following general formula (8A).
Figure BDA0001767876040000161
(in the formula (8A), n1 represents an integer of 0 to 10, R 8A1 Is an aliphatic group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, R 8A2 Each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group. )
R 8 The phenylene group in (1) may have a substituent or may form a fused ring. The phenylene group is preferably represented by the following general formula (8B).
Figure BDA0001767876040000162
(in the formula (8B), n2 represents an integer of 0 to 4, R 8B1 Each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group. )
R 8 The group having a diphenylene skeleton bonded with an alkylene group in (1) may have a substituent or may form a fused ring. The group having a phenylene skeleton bonded with an alkylene group is preferably represented by the following general formula (8C).
Figure BDA0001767876040000163
(in the formula (8C), n3 and n4 each independently represent an integer of 0 to 4, and R 8C1 And R 8C2 Each independently represents an aliphatic group or an aromatic group, preferably an aliphatic group such as methyl or ethyl, R 8C3 Represents an alkylene group having 1 to 5 carbon atoms. )
R in the formula (8C) 8C3 The alkylene group (b) may have a substituent such as an aliphatic group or an aromatic group.
R 8 The alkylene group in (1) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. In addition, R is 8 The alkylene group in (2) may have a substituent such as an aliphatic group or an aromatic group.
For excellent resolution, R 8 The group having an alicyclic skeleton is preferable, and the group having an alicyclic skeleton and no aromatic skeleton is more preferable.
In the present invention, R in the formula (4-1) 9-1 And R 10-1 Each independently a 1-valent organic group or a functional group having silicon. As R 9-1 And R 10-1 Examples of the organic group having a valence of 1 in (1) include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. As R 9-1 And R 10-1 Examples of the 1-valent silicon-containing functional group in (2) include a siloxane group, a silane group, and a silanol group.
R in the formula (4-1) from the viewpoint of solubility at the time of synthesis of polyamic acid ester 9-1 And R 10-1 Alkyl groups are preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Alkyl is here preferably butyl, pentyl or hexyl.
In the present invention, R in the formula (4-1) 11 Examples of the organic group having a valence of 2 include groups at least partially composed of an aromatic or aliphatic ester group, an amide imide group, a siloxane group, an epoxy group, an oxetane group, and the like.
Other components that can be blended in the photosensitive resin composition of the present invention will be described below.
The solvent that can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve the photobase generator, the polymer precursor, and other additives. Examples thereof include N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazoline, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, and diethylene glycol monomethyl ether. These may be used alone, or 2 or more kinds may be mixed and used. The amount of the solvent to be used is not particularly limited, and may be, for example, 50 to 9000 parts by mass per 100 parts by mass of the polymer precursor depending on the coating film thickness and viscosity.
In order to further improve the photosensitivity, a sensitizer may be added to the photosensitive resin composition of the present invention. Examples of the sensitizer include Michler's ketone, 4 ' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 ' -dimethylaminobenzylidene) -4-methylcyclohexanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 4 ' -bis (dimethylamino) chalcone, 4 ' -bis (diethylamino) chalcone, p-dimethylaminocinnamoindanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminobhenylbiphenylene) -benzothiazole, 2- (p-dimethylaminobenylvinylene) benzothiazole, 2- (p-dimethylaminobenylidene) benzothiazole, 2-bis (4 ' -dimethylaminobenzylidene) -4-methylcyclohexanone, and p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1, 3-bis (4 '-dimethylaminobenzylidene) propanone, 1, 3-bis (4' -diethylaminobenzylidene) propanone, 3 '-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, and mixtures thereof, N-phenylethanolamine, 4-morpholinobenzophenone, 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-dimethylaminostyryl) styrene and the like, and a thioxanthone such as 4- (1-methylethyl) -9H-thioxanthen-9-one is preferably used from the viewpoint of sensitivity. These may be used alone or in combination of 2 to 5 kinds. The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the polymer precursor.
In addition, an adhesion promoter may be added to the photosensitive resin composition of the present invention in order to improve adhesion to a substrate. As the adhesion promoter, a known adhesion promoter may be used as long as it does not depart from the gist of the present invention. Examples thereof include γ -aminopropyldimethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropylmethyldimethoxysilane, γ -glycidoxypropylmethyldimethoxysilane, γ -mercaptopropylmethyldimethoxysilane, N- [3- (triethoxysilyl) propyl ] phthalimidoic acid, and a reaction product of benzophenone tetracarboxylic dianhydride with (triethoxysilyl) propylamine. The amount of the adhesion promoter is preferably in the range of 0.5 to 10 parts by mass per 100 parts by mass of the polymer precursor.
In addition, an alkali proliferation agent may be added to the photosensitive resin composition of the present invention. When forming a thick film pattern, the same degree of decomposition rate of the photobase generator is required from the surface to the lower side. In this case, it is preferable to add an alkali growth promoter in order to improve the sensitivity. For example, the alkali proliferating agents disclosed in Japanese patent laid-open Nos. 2012 and 237776 and 2006 and 282657 can be used.
The photosensitive resin composition of the present invention may contain other photosensitive components that generate an acid by light, within a range that does not significantly impair the film characteristics after curing. When a compound having 1 or 2 or more ethylenically unsaturated bonds is added to the photosensitive resin composition of the present invention, a photoradical generator may be added.
In order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles, and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and they may have a porous or hollow structure. Specific materials for obtaining porous shapes and hollow structures include various pigments, fillers, fibers, and the like.
The dry film of the present invention has a resin layer obtained by applying the photosensitive resin composition of the present invention on a carrier film (support) and drying the same. The dry film was formed as follows: the photosensitive resin composition of the present invention is diluted with the organic solvent to adjust the viscosity to an appropriate level, and then coated on a carrier film to a uniform thickness by a comma coater, a knife coater, a lip coater, a bar coater, a pressure coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like. Then, the coated photosensitive resin composition is dried at a temperature of 50 to 130 ℃ for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, and is generally selected appropriately within a range of 10 to 150 μm, preferably 20 to 60 μm, in terms of the film thickness after drying.
As the carrier film, a plastic film is used, and preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like is used. The thickness of the carrier film is not particularly limited, and is generally selected as appropriate within the range of 10 to 150 μm.
After forming a resin layer containing the photosensitive resin composition of the present invention on a carrier film, a protective film that can be peeled off is preferably laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. Examples of the peelable protective film include a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, and surface-treated paper. The protective film may be peeled off from the carrier film with less adhesion force between the resin layer and the carrier film.
Next, a method for producing a patterned film as a cured product using the photosensitive resin composition of the present invention will be described, as an example, with respect to a case where a polyamic acid ester as a polyimide precursor is blended as a polymer precursor.
First, as step 1, a photosensitive resin composition is applied onto a substrate and dried to obtain a coating film. As a method for applying the photosensitive resin composition to the substrate, a method used in the conventional application of the photosensitive resin composition, for example, a method of applying the photosensitive resin composition by 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; and an ink jet method. As a method for drying the coating film, a method such as air drying, heat drying in an oven or a hot plate, or vacuum drying is used. Further, it is desirable that the drying of the coating film is carried out under the condition that imidization of the polyamic acid ester in the photosensitive resin composition does not occur. Specifically, the drying may be carried out by natural drying, air-blowing drying or heat drying at 20 to 140 ℃ for 1 minute to 1 hour. Preferably, drying is carried out on a hot plate for 1 to 20 minutes. Further, vacuum drying may be performed, and in this case, drying may be performed at room temperature for 1 minute to 1 hour.
The base material is not particularly limited, and can be widely used for silicon wafers, wiring boards, various resins, metals, passivation films of semiconductor devices, and the like.
Further, since imidization can be performed at a low temperature, it is widely used for members and materials which are not suitable for high-temperature treatment, such as substrates of printed wiring boards.
Next, as step 2, the coating film is exposed through a photomask having a pattern or directly exposed. The exposure light is light having a wavelength which activates the photobase generator to generate a base. When a sensitizer is used as appropriate as described above, the photosensitivity can be adjusted. As the exposure device, a contact aligner, a mirror projection, a step exposure device, a laser line exposure device, or the like can be used.
Next, as step 3, heating is performed so as to accelerate imidization of the coating film by the alkali generated in the coating film. Thus, the base generated in the exposed portion in the step 2 serves as a catalyst, and the polyamic acid ester is partially imidized. The heating time and heating temperature are appropriately changed depending on the polyamic acid ester to be used, the coating film thickness, and the type of photobase generator. Typically, the coating thickness of about 10 μm is about 2 to 10 minutes at 110 to 200 ℃. When the heating temperature is too low, partial imidization cannot be effectively achieved. On the other hand, if the heating temperature is too high, imidization of the unexposed portions proceeds, and the difference in solubility between the exposed portions and the unexposed portions is reduced, which may hinder pattern formation.
Next, as step 4, the coating film is treated with a developer. Thereby, a pattern film containing a polyamic acid ester and a partially imidized polyimide can be formed on the substrate.
As a method used for the development, any method can be selected from conventionally known developing methods of photoresists, for example, spin coating, paddle method, dipping method with ultrasonic treatment, and the like. Examples of the developer include aqueous solutions of inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, or isopropyl alcohol, or a surfactant may be added to the mixture to form an aqueous solution. Thereafter, the coating film is washed with a washing liquid as necessary to obtain a patterned film. As the washing liquid, it can be used alone or in combination: distilled water, methanol, ethanol, isopropanol, and the like.
Further, as the developer, for example, organic solvents such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, γ -butyrolactone, hexamethylphosphoric triamide, methanol, ethanol, isopropanol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate, diacetone alcohol and the like can be used.
Thereafter, as step 5, the pattern film is heated. The heating temperature is appropriately set so that the polyimide pattern film can be cured. For example, the heating is performed in an inert gas at 150 to 300 ℃ for about 5 to 120 minutes. The heating temperature is more preferably in the range of 150 to 250 ℃, and still more preferably in the range of 180 to 220 ℃. The heating is performed by using, for example, a hot plate, an oven, or a temperature-raising oven capable of setting a temperature program. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.
The application of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include various known fields and products using resin materials such as printing inks, adhesives, fillers, electronic materials, optical circuit components, molding materials, resist materials, building materials, three-dimensional shapes, optical members, and the like. In particular, the polyimide film is suitable for use as a material for forming a wide range of fields and products in which properties such as heat resistance, dimensional stability, and insulation property of polyimide films are considered to be effective, for example, a paint or a printing ink, a wiring cover film such as a color filter, a thin film for a flexible display, a semiconductor device, an electronic component, an interlayer insulating film, and a solder resist, an optical circuit component, an antireflection film, a hologram, an optical member, or a building material.
In particular, when a polyimide precursor is contained as a polymer precursor, the photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern film formed therefrom functions as a component for imparting heat resistance and insulation properties as a permanent film containing polyimide, and is suitable for forming, for example, a color filter, a film for flexible display, an electronic component, a semiconductor device, an interlayer insulating film, a solder resist, a wiring cover film such as a cover film, a tin bank, an optical circuit component, an antireflection film, other optical components, or an electronic component.
In the present invention, the alkali-producing agent may be produced by mixing a carboxylic acid represented by the following general formula (8) with an alkali.
Figure BDA0001767876040000221
The carboxylic acid is more preferably a carboxylic acid represented by the following general formula (9), and still more preferably 4-methoxy-3-nitrophenylacetic acid (MONPA) represented by the following formula (10).
Figure BDA0001767876040000222
Figure BDA0001767876040000231
In the formulae (8) and (9), R 1 ～R 4 、X 1 、X 2 Y is the same as in the above general formula (1).
As the base, a base represented by B in the general formula (1) can be used.
The carboxylic acid and the base are preferably mixed by dropping a solution of the base into a solution of the carboxylic acid while keeping the carboxylic acid away from light.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the following, all of the "parts" and "%" are based on mass unless otherwise specified.
[ Synthesis of Carboxylic acid ]
(reference Synthesis example 1: Synthesis of 4-methoxy-3-nitrophenylacetic acid (MONPA))
In a 500ml two-necked eggplant type flask, 30ml of concentrated nitric acid (67 mass%) and 3.32g (20.0mmol) of 4-methoxyphenylacetic acid (MOPA) were mixed at 0 ℃ and stirred (room temperature, 6 hours). The resulting mixture was added dropwise to cold water, followed by suction filtration and washing with cold water to obtain 4-methoxy-3-nitrophenylacetic acid (MONPA) (yield: 2.51g, yield: 60%) as a pale yellow solid.
[ Synthesis of photobase generators ]
Example 1-1 Synthesis of MOMPA-TBD)
In a 50ml eggplant type bottle, 0.300g (1.42mmol) of 4-methoxy-3-nitrophenylacetic acid (MONPA) synthesized in the above dissolved in 10ml of dry ethanol, and 1,5, 7-triazabicyclo [4.4.0] dissolved in 10ml of dry ethanol]0.198g (1.42mmol) of-5-decene (TBD) was mixed and stirred at room temperature for evening-out. The resulting mixture was concentrated with EtOH/Et 2 O was reprecipitated to obtain MOMPA-TBD as an orange viscous liquid (yield: 0.289g, yield: 58%). Will be provided with 1 H-NMR(300MHz、CDCl 3 ) Is shown in FIG. 1, and the peak is shownThe analysis results are shown below.
δ1.96(quint,J＝5.9Hz,4H,-CH 2 -),3.1-3.4(m,8H,-NCH 2 -),3.53(s,2H,Bn-H),3.92(s,3H,-OCH 3 ),7.00(d,J＝8.6Hz,1H,Ar-H),7.51(dd,J＝8.6,2.2Hz,1H,Ar-H),7.85(d,J＝2.2Hz,1H,Ar-H),10.64(br,1.4H,NH).
Examples 1-2 Synthesis of MOMPA-DBU
The 1,5, 7-triazabicyclo [4.4.0] in Synthesis example 1]MOMPA-DBU was obtained as an orange viscous liquid in the same manner as in Synthesis example 1 except that 0.198g (1.42mmol) of-5-decene (TBD) was changed to 0.216g (1.42mmol) of Diazabicycloundecene (DBU) (yield: 0.419g, yield: 81%). Will be provided with 1 H-NMR(300MHz、CDCl 3 ) Fig. 2 shows the results of peak analysis, which are described below.
δ1.6-1.8(m,6.7H,-CH 2 -),1.99(quint,J＝6.0Hz,2H,-CH 2 -),2.7-2.9(m,2H,-CH 2 -),3.3-3.5(m,6H,-NCH 2 -),3.56(s,2H,Bn-H),3.92(s,3H,-OCH 3 ),6.99(d,J＝8.6Hz,1H,Ar-H),7.53(dd,J＝8.6,2.2Hz,1H,Ar-H),7.86(d,J＝2.2Hz,1H,Ar-H).
Examples 1-3 Synthesis of MOMPA-2E4MZ
The 1,5, 7-triazabicyclo [4.4.0] in Synthesis example 1]In the same manner as in Synthesis example 1 except for changing 0.198g (1.42mmol) of (E) -5-decene (TBD) to 0.156g (1.42mmol) of 2-ethyl-4-methylimidazole (2E4MZ), MOMPA-2E4MZ (yield: 0.186g, 41%) was obtained as an orange viscous liquid. Will be provided with 1 H-NMR(300MHz、CDCl 3 ) The graph of (a) is shown in fig. 3, and the analysis result of the peak is shown below.
δ1.12(t,J＝7.6Hz,6H,-CH 2 CH 3 ),2.15(s,3H,-CH 3 ),2.65(q,J＝7.6Hz,2H,-CH 2 CH 3 ),3.61(s,2H,Bn-H),3.93(s,3H,-OCH 3 ),6.56(s,1H,Im-H),7.01(d,J＝8.6Hz,1H,Ar-H),7.48(dd,J＝8.6,2.2Hz,1H,Ar-H),7.82(d,J＝2.2Hz,1H,Ar-H).
Examples 1 to 4 Synthesis of MOMPA-DBA
The 1,5, 7-triazabicyclo [4.4.0] in Synthesis example 1]0.198g (1) of-5-decene (TBD).42mmol) was changed to Dibutylamine (DBA)0.184g (1.42mmol), and MOMPA-DBA was obtained as an orange solid in the same manner as in Synthesis example 1 (yield: 0.473g, yield: 98%). Will be provided with 1 H-NMR(300MHz、CDCl 3 ) Fig. 4 shows the results of peak analysis, which are described below.
δ0.86(t,J＝7.3Hz,6H,-CH 3 ),1.26(sext,J＝7.3Hz,4H,-CH 2 -),1.4-1.6(m,4H,-CH 2 -),2.6-2.7(m,4H,-CH 2 -),3.47(s,2H,Bn-H),3.93(s,3H,-OCH 3 ),6.99(d,J＝8.6Hz,1H,Ar-H),7.44(dd,J＝8.6,2.2Hz,1H,Ar-H),7.81(d,J＝2.2Hz,1H,Ar-H).
Comparative example 1-1 Synthesis of photobase generator described in Japanese patent No. 4830435
Ketoprofen (5.09 g, 20mmol) and 1.12g (10mmol) of 1, 4-diazabicyclo [2.2.2] octane were placed in a flask, the flask was heated at 50 ℃ and cyclohexane was slowly added until ketoprofen and 1, 4-diazabicyclo [2.2.2] octane were completely dissolved. After that, upon cooling, a white precipitate was obtained. The mixture was dried at 45 ℃ for 2 hours under reduced pressure to obtain the photobase generator shown below.
Figure BDA0001767876040000251
[ measurement of molar absorptivity of photobase generators ]
The photobase generators synthesized in the above were measured for UV-vis spectrum using MultiSpec-1500 (product of Shimadzu corporation) and molar absorption coefficient under i-ray (365nm) was measured. The solution cuvette used was a cuvette made of quartz and having an optical path length of 1 cm. The molar absorption coefficient is a value obtained by dividing the absorbance of the solution by the thickness of the absorbing layer and the molar concentration of the solute. The results are shown in Table 1.
[ Table 1]
Figure BDA0001767876040000252
It is found that the photobase generators of examples 1-1 to 1-4 satisfying the general formula (1) have a high molar absorption coefficient under the i-ray.
[ evaluation of Heat resistance of photobase generators ]
The photobase generator (MONPA-TBD) of example 1-1 was subjected to TG-DTA measurement (temperature increase rate 5 ℃ C./min) using TG-DTA2000S manufactured by Mac Science, and it was confirmed that the photobase generator was stable up to around 200 ℃.
[ Synthesis of Polyamic acid ester ]
(Synthesis example 1 Synthesis of Polyamic acid ester A-1)
To 5g of 6FDA (4, 4' - (hexafluoroisopropylidene) diphthalic anhydride) as an acid dianhydride was added about 25g of dry t-butanol and refluxed. Approximately 30 minutes after the start of reflux, a substantially clear liquid was obtained. Further, the mixture was refluxed for about 5 hours, cooled, and filtered through a filter having a pore diameter of 0.7 μm to remove impurities. The reaction mixture was dried under reduced pressure to completely remove t-butanol, and the half ester of an acid anhydride described in Table 1 was obtained as white crystals.
A three-necked flask having a capacity of 100ml was charged with 5mmol of the half ester of an acid anhydride described in Table 1 and 0.0125mmol of anhydrous 3-methyl-1-phenyl-2-phosphole 1-oxide, and the mixture was dissolved in 10ml of dehydrated sulfolane while flowing nitrogen. 5mmol of anhydrous ITI (isophorone diisocyanate) as a diisocyanate was dissolved in 5ml of dehydrated sulfolane, and the solution was added dropwise to the flask over about 5 minutes. The mixed solution was reacted at 200 ℃ for 3 hours, and precipitated with MeOH (500 ml). The solution containing the precipitate was filtered and dried to obtain a high molecular precursor polymer. The resulting polymer was dissolved in DMAc (N, N-dimethylacetamide) and reprecipitated with MeOH. After filtration and drying, a 15 mass% polyamic acid ester A-1 solution was prepared using dehydrated DMAc as a solvent.
[ Table 2]
Figure BDA0001767876040000261
(Synthesis example 2 Synthesis of Polyamic acid ester A-2)
A polyamic acid ester A-2 solution was prepared in the same manner as in Synthesis example 1 except that 6FDA was changed to TDA (1,3,3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-c ] furan-1, 3-dione).
[ Table 3]
Figure BDA0001767876040000271
Synthesis example 3 Synthesis of polyamic acid ester A-3
7.75g of 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.86g of 4,4 ' -diaminodiphenyl ether (DDE) were dissolved in 30g of N-methylpyrrolidone (NMP), and stirred at 60 ℃ for 4 hours, followed by stirring at room temperature for methylo-e-p-methylo. To this, 9.45g of trifluoroacetic anhydride was added under water cooling, and stirred at room temperature for 3 hours, followed by addition of 1.73g of ethanol. The reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to prepare a solution of polyamic acid ester A-3. The number average molecular weight of the polyamic acid ester A-3 was 27000.
(example 2-1)
The photobase generator was mixed and dissolved in the solution of the polyamic acid ester obtained in the above manner at a mixing ratio (mass ratio) described in the following table to obtain photosensitive resin compositions of examples and comparative examples. The compounding amount of the polyamic acid ester in the table indicates the amount of the solid component.
The photosensitive resin composition of example 2-1 in the following table was coated on a 4-inch silicon wafer by spin coating, and heated on a hot plate at 80 ℃ for 20 minutes to form a photosensitive resin composition film having a thickness of 10 μm. The film is exposed to light at a wavelength of 0 to 1000mJ/cm through a mask pattern by using a high-pressure mercury lamp exposure device equipped with an i-ray filter 2 The exposure is performed with a light amount in the range of (1). After exposure, the substrate was heated on a hot plate at 140 ℃ for 10 minutes, and then immersed in a solvent at a weight ratio of 1: 1A developer containing a 2.38% aqueous solution of tetramethylammonium hydroxide and 2-propanol was mixed for 90 seconds, and the mixture was further washed with water for 20 seconds to develop a pattern.
As a result, it was confirmed that the exposure dose was 150mJ/cm 2 The above light is irradiated to form a pattern.
(examples 2-2 to 2-9 and comparative examples 2-1 to 2-3)
By the same procedure as in example 2-1, a development test was carried out at a compounding ratio (mass ratio) and an exposure amount shown in the following table, and the exposure amount for pattern formation was confirmed.
[ Table 4]
Figure BDA0001767876040000281
*1: at 1000mJ/cm 2 The patterning cannot be performed.
It is understood that the photosensitive resin composition of the example containing the photobase generator satisfying the general formula (1) is excellent in sensitivity and excellent in pattern formability although it is a curing condition at a low temperature.

Claims (9)

1. A photosensitive resin composition comprising: an ionic photobase generator comprising a carboxylic acid represented by the following general formula (1) and a base,
the photosensitive resin composition further contains a polymer precursor, wherein the polymer precursor is at least one of polyamic acid and polyamic acid ester,
Figure FDA0003520361940000011
in the formula (1), R 1 ～R 4 Each independently being a hydrogen atom or a substituent, X 1 And X 2 One of them is an electron withdrawing group, the other is a hydrogen atom, Y is an electron donating group, B represents a base,
the substituent is a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silyl group, a silanol group, a cyano group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphate group, a phosphono group, a phosphonate group, an alkoxy group or an amide group,
the electron-withdrawing group is selected from the group consisting of-C ≡ N, -COCH 3 、-NO 2 -F, -Cl, -Br and-I,
the power supplyThe sub-group being selected from the group consisting of-CH 3 、-C 2 H 5 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-C 6 H 5 、-OH、-OCH 3 and-OC 6 H 5 A group of components selected from the group consisting of,
the base is a secondary amine, a tertiary amine or a nitrogen-containing cyclic compound.
2. The photosensitive resin composition according to claim 1, wherein the molar absorption coefficient of the photobase generator is 300L-mol -1 ·cm -1 The above.
3. The photosensitive resin composition according to claim 1, wherein the polymer precursor is a polyamic acid ester having a structure represented by the following general formula (4-1),
Figure FDA0003520361940000021
in the formula (4-1), R 7 Is a 4-valent organic radical, R 8 R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group 9-1 And R 10-1 Optionally identical to or different from one another, are organic radicals having a valence of 1 or functional groups having silicon, R 11 Is an organic group having a valence of 2, m is an integer of 1 or more, and n is 0 or an integer of 1 or more.
4. The photosensitive resin composition according to claim 3, wherein R in the general formula (4-1) 7 Is a 4-valent organic group containing a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, a 4-valent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a 4-valent organic group containing a fluorine atom.
5. The photosensitive resin composition according to claim 4, wherein the polymer precursor is a polyamic acid ester having a structure represented by at least one of the following general formulae (4-1-1) and (4-1-2),
Figure FDA0003520361940000022
in the formula (4-1-1), R 8 R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group 9-1 And R 10-1 Optionally identical to or different from one another, are organic radicals having a valence of 1 or functional groups having silicon, R 11 Is an organic group having a valence of 2, m is an integer of 1 or more, n is 0 or an integer of 1 or more,
Figure FDA0003520361940000031
in the formula (4-1-2), R 8 R is any of a group having an alicyclic skeleton, a phenylene group, a group having a diphenylene skeleton bonded with an alkylene group, and an alkylene group 9-1 And R 10-1 Optionally identical to or different from one another, are organic radicals having a valence of 1 or functional groups having silicon, R 11 Is a 2-valent organic group, m is an integer of 1 or more, and n is an integer of 0 or 1 or more.
6. A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 1 to a film and drying the applied film.
7. A cured product obtained by curing the resin layer of the photosensitive resin composition according to any one of claims 1 to 5 or the dry film according to claim 6.
8. A printed wiring board comprising the cured product according to claim 7.
9. A photobase generator characterized by being an ionic type formed by a carboxylic acid represented by the following general formula (1) and a base,
Figure FDA0003520361940000032
in the formula (1), R 1 ～R 4 Each independently being a hydrogen atom or a substituent, X 1 And X 2 One of them is an electron withdrawing group, the other is a hydrogen atom, Y is an electron donating group, B represents a base,
the substituent is a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silyl group, a silanol group, a cyano group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphate group, a phosphono group, a phosphonate group, an alkoxy group or an amide group,
the electron-withdrawing group is selected from the group consisting of-C ≡ N, -COCH 3 、-NO 2 -F, -Cl, -Br and-I,
said electron donating group is selected from the group consisting of-CH 3 、-C 2 H 5 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-C 6 H 5 、-OH、-OCH 3 and-OC 6 H 5 A group of (a) a group of (b),
the base is a secondary amine, a tertiary amine or a nitrogen-containing cyclic compound.
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