CN116609998A - Polyimide precursor, negative photosensitive resin composition, and method for producing cured relief pattern using same - Google Patents

Polyimide precursor, negative photosensitive resin composition, and method for producing cured relief pattern using same Download PDF

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CN116609998A
CN116609998A CN202310124490.5A CN202310124490A CN116609998A CN 116609998 A CN116609998 A CN 116609998A CN 202310124490 A CN202310124490 A CN 202310124490A CN 116609998 A CN116609998 A CN 116609998A
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photosensitive resin
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resin composition
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carbon atoms
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藤冈孝亘
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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
    • G03F7/16—Coating processes; Apparatus therefor
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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

Abstract

Polyimide precursor, negative photosensitive resin composition and method for producing polyimide precursorA method of manufacturing a cured relief pattern using the same. A negative photosensitive resin composition comprising: (A) A polyimide precursor comprising a structural unit represented by the general formula (1) and (B) a solvent. In the formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure. R is R 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure, OR 1 And OR 2 At least one of the groups is a monovalent organic group having a proportion of hetero atoms other than hydrogen atoms of 42% or more.

Description

Polyimide precursor, negative photosensitive resin composition, and method for producing cured relief pattern using same
Technical Field
The present application relates to a polyimide precursor, a negative photosensitive resin composition, a method for producing a cured relief pattern using the same, and the like.
Background
Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for insulating materials for electronic parts, passivation films for semiconductor devices, surface protective films, interlayer insulating films, and the like. Among the polyimide resins, particularly polyimide resins provided in the form of photosensitive polyimide precursor compositions can easily form a heat-resistant relief pattern coating film by coating, exposing, developing and curing (cure) based thermal imidization treatment of the compositions. The photosensitive polyimide precursor composition has a feature that the process can be greatly shortened as compared with conventional non-photosensitive polyimide materials.
However, 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 wire bonding methods in which thin wires are used to connect external terminals (pads) of the devices to lead frames. However, with the increase in the speed of the element, today, the operating frequency has reached GHz, and the difference in wiring length of each terminal in mounting has reached a level that affects the operation of the element. Therefore, in the component mounting for high-end use, it is necessary to accurately control the length of the mounting wiring, and it is difficult to satisfy the requirement in wire bonding.
Thus, there is proposed a flip chip mounting in which, after a rewiring layer is formed on the surface of a semiconductor chip and bumps (electrodes) are formed thereon, the chip is flipped (flipped) and directly mounted on a printed substrate. The flip chip mounting is used for a high-end element for processing a high-speed signal by accurately controlling a wiring distance, or is used for a mobile phone or the like by reducing a mounting size, and a demand thereof is rapidly expanding. Further, recently, a semiconductor chip mounting technology called fan-out wafer level package (FOWLP) has been proposed in which a wafer subjected to a preceding step is diced to produce individual chips, the individual chips are reconstructed on a support, the support is sealed with a mold resin, and a rewiring layer is formed after the support is peeled off. Fan-out wafer level packaging has the following advantages: in addition to the reduction in thickness of the package, the high-speed transfer and the low cost can be realized.
Prior art literature
Patent literature
Patent document 1: international publication No. 2021/215374
Patent document 2: international publication No. 2020/189358
Patent document 3: international publication No. 2017/038598
Patent document 4: international publication No. 2020/026840
Disclosure of Invention
Problems to be solved by the invention
In the case of using a negative photosensitive polyimide, examples of problems include: in the curing process (cure process), the photosensitive side chains released from the polyimide precursor remain in the polyimide film, which prevents interaction between the copper substrate and the polyimide resin, and thus the adhesion is reduced. On the other hand, if the released photosensitive side chains volatilize from the film, curing shrinkage during the curing process is significantly accelerated, and therefore, a technique is required in which the photosensitive side chains remain in the polyimide film without deteriorating the adhesion.
Known are: for adhesion of the polyimide film to the copper substrate, an anticorrosive agent having a heterocyclic structure is effective. For example, in patent document 1, an additive having a heterocyclic structure is used to improve adhesion to a substrate. However, the technology of patent document 1 does not aim at achieving both adhesion to a substrate and suppression of cure shrinkage during a curing process.
Patent document 2 has attempted to improve adhesion to a substrate by introducing a heterocyclic structure into a terminal structure or a side chain structure of a polymer. However, the objective of introducing a heterocyclic structure into a terminal structure is not to achieve both adhesion to a substrate and curing shrinkage during curing, but to introduce a heterocyclic structure into a side chain structure via an amide bond, which inhibits imidization during curing.
Accordingly, an object of the present application is to provide a negative photosensitive resin composition which can sufficiently promote imidization in a curing process, has good adhesion to copper wiring, and can suppress curing shrinkage in the curing process; and a method for producing a cured relief pattern using the negative photosensitive resin composition.
Solution for solving the problem
Hereinafter, examples of embodiments of the present application are given.
[1] A negative photosensitive resin composition comprising:
(A) A polyimide precursor comprising a structural unit represented by the following general formula (1); and
(B) And (3) a solvent.
{ in formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure, wherein R 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure. }
[2] A negative photosensitive resin composition comprising:
(A) A polyimide precursor comprising a structural unit represented by the following general formula (1); and
(B) And (3) a solvent.
{ in formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure, wherein OR 1 And OR 2 At least one of the groups is a monovalent organic group having a proportion of hetero atoms other than hydrogen atoms of 42% or more. }
[3] The negative-working photosensitive resin composition according to item 1 or 2, further comprising (C) a photopolymerization initiator.
[4]The negative photosensitive resin composition according to any one of items 1 to 3, wherein R 1 And R is 2 At least one of them is a monovalent organic group comprising a heterocyclic structure comprising a nitrogen atom.
[5]The negative photosensitive resin composition according to any one of items 1 to 4, wherein R 1 And R is 2 At least one of them is a monovalent organic group comprising a five-membered ring heterocyclic structure comprising a nitrogen atom.
[6]The negative photosensitive resin composition according to any one of items 1 to 5, wherein R is R in all the structural units of the polyimide precursor (A) 1 And R is 2 At least one of them has a (meth) acrylate group.
[7]The negative photosensitive resin composition according to any one of items 1 to 6, wherein R is R in all the structural units of the polyimide precursor (A) 1 And R is 2 The total of two or more (meth) acrylate groups.
[8]The negative photosensitive resin composition according to any one of items 1 to 7, wherein,R 1 and R is 2 At least one of them is a group represented by the following general formula (3),
{ in formula (3), ar is the aforementioned heterocyclic structure; the dotted line is a single bond to the oxygen atom of formula (1); r is R 3 、R 4 And R is 5 Each independently is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; r is R 6 And R is 7 Each independently is a divalent organic group having 1 to 10 carbon atoms optionally containing a heteroatom. }
[9]The negative photosensitive resin composition according to any one of items 1 to 8, wherein R 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure, and the heterocyclic structure is triazole or tetrazole.
[10]The negative photosensitive resin composition according to any one of items 1 to 9, wherein R in the polyimide precursor (A) 1 And R is 2 More than 10 mol% of the whole has the heterocyclic structure and/or the structure with a high proportion of the hetero atoms.
[11] The negative photosensitive resin composition according to any one of items 1 to 10, further comprising (D) a monomer having a polymerizable functional group.
[12] The negative photosensitive resin composition according to any one of items 1 to 11, wherein the monomer having a polymerizable functional group (D) has 2 or more polymerizable functional groups.
[13] The negative photosensitive resin composition according to any one of items 1 to 12, wherein the monomer having a polymerizable functional group (D) has 3 or more polymerizable functional groups.
[14]The negative photosensitive resin composition according to any one of items 1 to 13, wherein X is 1 Comprises at least 1 selected from the group consisting of the following general formulae (8) to (11).
[15]The negative photosensitive resin composition according to any one of items 1 to 14, wherein Y is 1 Comprises at least 1 selected from the group consisting of the following general formulae (12) to (15).
{ in which R 11 Each independently is a monovalent organic group having 1 to 10 carbon atoms optionally containing a halogen atom; a is an integer of 0 to 4. }
[16] The negative photosensitive resin composition according to any one of items 1 to 15, further comprising 0.1 to 40 parts by mass of (E) a thermal alkali generator based on 100 parts by mass of the polyimide precursor (A).
[17] A method of manufacturing a cured relief pattern comprising the steps of:
(1) A step of applying the negative photosensitive resin composition according to any one of items 1 to 16 to a substrate, and forming a photosensitive resin layer on the substrate;
(2) Exposing the photosensitive resin layer;
(3) Developing the exposed photosensitive resin layer to form a relief pattern; and
(4) And a step of heating the relief pattern to form a cured relief pattern.
[18] A polyimide precursor comprising a structural unit represented by the following general formula (1).
{ in formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a hetero atom；R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure, wherein R 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure. }
[19] A polyimide precursor comprising a structural unit represented by the following general formula (1).
{ in formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure, wherein OR 1 And OR 2 At least one of the groups is an organic group having a proportion of hetero atoms other than hydrogen atoms of 42% or more. }
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present application, there is provided a negative photosensitive resin composition capable of sufficiently promoting imidization in a curing process, having good adhesion to copper wiring, and suppressing curing shrinkage in the curing process; and a method for producing a cured relief pattern using the negative photosensitive resin composition.
Detailed Description
Hereinafter, embodiments of the present application will be described in detail. The present application is not limited to the following embodiments, and can be implemented by various modifications within the scope of the gist thereof. Throughout this specification, where there are multiple structures in the molecule represented by the same symbols in the formulae, they are optionally the same or different from each other.
< negative photosensitive resin composition >
The negative photosensitive resin composition of the present application is a negative photosensitive resin composition comprising:
(A) A polyimide precursor comprising a structural unit represented by the following general formula (1); and
(B) And (3) a solvent.
In the formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure. Wherein R is 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure, OR 1 And OR 2 At least one of the groups is a monovalent organic group having a proportion of the number of hetero atoms (hereinafter, also simply referred to as "hetero atom proportion") among constituent atoms other than hydrogen atoms of 42% or more. R is R 1 And R is 2 At least one of them may have a heterocyclic structure, and the heteroatom ratio may be 42% or more. In the calculation of the heteroatom ratio, R is included in the formula 1 And R is 2 An oxygen atom in the directly bonded ester bond (an oxygen atom derived from a side chain compound). Thus, when referring to the heteroatom ratio, this is expressed as "OR 1 Sum OR 2 ”。
While not being limited by theory, the negative photosensitive resin composition of the present application has an organic group having a heterocyclic structure and/or a structure with a high heteroatom ratio (hereinafter also referred to as "high heteroatom structure") in the side chain structure of the polymer, and thus the side chain liberated from the polyimide precursor in the curing process remains in the polyimide film, thereby being capable of suppressing cure shrinkage during the curing process and suppressing a decrease in copper adhesion due to the remaining side chain. In addition, the organic group having a heterocyclic structure and/or a high heteroatom structure of the side chain is bonded via an ester bond, not via an amide bond, whereby the imidization reaction in the aging process can be suppressed from being hindered. It can be considered that: as a result, imidization can be sufficiently promoted during the curing process, adhesion to copper wiring is good, and curing shrinkage during the curing process can be suppressed.
(A) Polyimide precursor
(A) The polyimide precursor is a resin component contained in the negative photosensitive resin composition, and is converted into polyimide by performing a thermal cyclization treatment. The polyimide precursor is a polyimide precursor having a structure represented by the above general formula (1).
In the general formula (1), X is used from the viewpoint of heat resistance and photosensitivity 1 The tetravalent organic group represented is preferably an organic group having 6 to 40 carbon atoms, more preferably-COOR 1 Radical and-COOR 2 An aromatic group or an alicyclic aliphatic group in which the groups are ortho to the-CONH-group. As X 1 Examples of the tetravalent organic group represented by the formula (X) include organic groups having 6 to 40 carbon atoms and containing an aromatic ring 1 -1) and (X) 1 -2) groups of the respective illustrated structure, but are not limited thereto.
(X) 1 -1) and (X) 1 -2) wherein R6 is selected from the group consisting of hydrogen, fluorine, C 1 ～C 10 Hydrocarbon radicals and C of (2) 1 ～C 10 A monovalent group of the group consisting of fluorocarbon groups; l is an integer selected from 0 to 2; m is an integer selected from 0 to 3; and n is an integer selected from 0 to 4. X is X 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, it is particularly preferable to have the above formula (X 1 -1) and (X) 1 -2) X of the structure shown in each case 1 The radical is more preferably a radical of the formula (X) 1 -1) the structures shown in each case.
As X 1 A radical of the formula (X) 1 Of the structures represented by the formula-1), the structures represented by the following formulae are particularly preferred from the viewpoints of imidization rate, outgassing, copper adhesion and chemical resistance.
Wherein R6 and m are each the same as those of the above formula (X) 1 R6 and m in 1) have the same meaning.
X is from the viewpoints of imidization rate, outgassing, copper adhesion and chemical resistance 1 More preferably at least 1 selected from the group consisting of the following general formulae (8) to (11).
In the general formula (1), Y is from the viewpoint of heat resistance and photosensitivity 1 The divalent organic group is preferably an aromatic group having 6 to 40 carbon atoms, and examples thereof include the following formula (Y) 1 -1) and (Y) 1 -2) the structures shown in each case, but are not limited to them.
(Y) 1 -1) and (Y) 1 -2) wherein R6 is selected from the group consisting of hydrogen, fluorine, C 1 ～C 10 Hydrocarbon radicals and C of (2) 1 ～C 10 A monovalent group selected from the group consisting of fluorocarbon groups and n is 0 to 104. 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, it is particularly preferable to have the above formula (Y 1 -1) and (Y) 1 -2) Y of the respective indicated structure 1 The radical is more preferably a radical of the formula (Y) 1 -1) the structures shown in each case.
As Y 1 A radical of the formula (Y) 1 Of the structures represented by the formula-1), the structures represented by the following formulae are particularly preferred from the viewpoints of imidization rate, outgassing, copper adhesion and chemical resistance.
Wherein R6 and n are each the same as those of the above formula (Y) 1 R6 and n in 1) have the same meaning.
From the viewpoints of imidization rate, outgassing, copper adhesion, and chemical resistance, Y 1 More preferably at least 1 selected from the group consisting of the following general formulae (12) to (15).
In the formulae (12) to (15), R 11 Each independently is optionally a monovalent organic group of 1 to 10 carbon atoms, such as a monovalent organic group of 1 to 5 carbon atoms or 1 to 3 carbon atoms, a hydrocarbon group or an alkyl group, optionally containing a halogen atom. a is an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, and may be 0.
R in the above general formula (1) 1 And R is 2 At least one of them is preferably a group comprising a polymerizable group selected from the group consisting of an acid polymerizable group, a base polymerizable group and a radical polymerizable group. Here, the acid-polymerizable group, the base-polymerizable group, and the radical-polymerizable group refer to groups that can be polymerized by the action of an acid, a base, or a radical, respectively.
From the viewpoint of adhesionStarting from (A) R in the polyimide precursor 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure. From the viewpoint of adhesion, R 1 And R is 2 The heteroatom ratio of at least one of these may be preferably 42% or more, more preferably 43% or more, and still more preferably 44% or more. The upper limit of the heteroatom ratio which can be combined with these lower limits is not particularly limited as long as it is less than 100%, and may be, for example, 60% or less, 55% or less, or 50% or less.
R 1 And R is 2 The monovalent organic group having 1 to 40 carbon atoms may preferably have a heterocyclic structure and/or a high heteroatom structure, and from the viewpoint of resolution, the monovalent organic group having 1 to 40 carbon atoms is preferably a group represented by the following general formula (2).
In the formula (2), R 3 、R 4 And R is 5 Each independently is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 1 Is an integer of 1 to 10, preferably an integer of 1 to 5 or an integer of 1 to 3. For example, the group represented by the general formula (2) is preferably a group represented by the following formula.
Wherein R is 3 、R 4 And R is 5 Each independently represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. Examples of the monovalent organic group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and the like. R is R 3 Preferably hydrogen or methyl, R 4 And R is 5 Preferably a hydrogen atom.
R 1 And R is 2 At least one of them, preferably a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure, is not particularly limited, from the viewpoint of inhibitionIn view of curing shrinkage during the curing process, it is preferable that the resin further has a (meth) acryloyl group. For example, R 1 And R is 2 At least one of them is more preferably a group represented by the following general formula (3).
In the formula (3), ar is a heterocyclic structure; the dotted line is a single bond to the oxygen atom of formula (1); r is R 3 、R 4 And R is 5 Each independently is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; r is R 6 And R is 7 Each independently is a divalent organic group having 0 to 10 carbon atoms optionally containing a heteroatom, preferably a divalent organic group having 1 to 10 carbon atoms optionally containing a heteroatom, a divalent organic group having 1 to 5 carbon atoms, or a divalent organic group having 1 to 3 carbon atoms.
Examples of the monovalent organic group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and the like. R is R 3 Preferably hydrogen or methyl, R 4 And R is 5 Preferably a hydrogen atom. Examples of the divalent organic group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and structural isomers thereof. R is R 6 And R is 7 Each independently is preferably a group selected from the group consisting of a divalent organic group having 1 to 3 carbon atoms containing a thioether bond, a methylene group, an ethylene group, and a propylene group, and more preferably a divalent organic group having 1 to 3 carbon atoms containing a thioether bond or a methylene group.
Preferably, it is: in at least one structural unit of the polyimide precursor (A), R 1 And R is 2 At least one of them has a (meth) acrylate group, more preferably: in all structural units of the polyimide precursor (A), R 1 And R is 2 At least one of them has a (meth) acrylate group. Preferably, it is: in at least one structural unit of the polyimide precursor (A), R 1 And R is 2 Both of them have a (meth) acrylate group, more preferably: in all structural units of the polyimide precursor (A), R 1 And R is 2 The total of two or more (meth) acrylate groups. Namely means that: may be R 1 Having more than two (meth) acrylate groups, and R 2 Does not have a (meth) acrylate group, or may be R 1 Does not have (meth) acrylate groups, R 2 Having more than two (meth) acrylate groups, or, alternatively, R 1 Having more than 1 (meth) acrylate group, R 2 Also has 1 or more (meth) acrylate groups, whereby R 1 And R is 2 The total of two or more (meth) acrylate groups. By letting R 1 And R is 2 The reason why the curing shrinkage at the time of the curing process is suppressed by preferably having a (meth) acryloyl group in at least one of the side chains having a heterocyclic structure and/or a high heteroatom structure is not limited by theory, but the inventors believe that the reason is that the volatilization of the photosensitive side chain released from the polyimide precursor during the curing process is suppressed by the thermal polymerization of the (meth) acryloyl group, and thus the curing shrinkage is suppressed.
From the viewpoint of adhesion, R 1 And R is 2 At least one of them, preferably a monovalent organic group having a heterocyclic structure and/or a high heteroatom structure, is preferably a monovalent organic group comprising a heterocyclic structure, the heterocyclic structure comprising a nitrogen atom, more preferably a monovalent organic group comprising a five-membered ring heterocyclic structure, the five-membered ring heterocyclic structure comprising a nitrogen atom. The heterocyclic structure is preferably a triazole or tetrazole structure from the viewpoint of adhesion.
From the viewpoint of copper adhesion, R is 1 And R is 2 The proportion of monovalent organic groups having a heterocyclic structure and/or a high heteroatom structure is preferably 10 mol% or more based on the total number of moles of the groups. By introducing 10 mol% or more, copper adhesion is further improved.
(A) Method for producing polyimide precursor
As a method for producing the polyimide precursor (A), there can be mentionedThe following methods are exemplified: containing the tetravalent organic group X 1 The tetracarboxylic dianhydride of (a) is reacted with an alcohol having a polymerizable group selected from the group consisting of an acid polymerizable group, a base polymerizable group and a radical polymerizable group, and optionally other alcohols to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester). Next, a tetracarboxylic acid (acid/ester) partially esterified with a compound containing the above-mentioned divalent organic group Y 1 Amide polycondensation of the diamine of (a) is performed to obtain (a) a polyimide precursor. As the direction R 1 And R is 2 By, for example, introducing at least one of the above-mentioned tetravalent organic groups X into a heterocyclic structure and/or a high heteroatom structure 1 The tetracarboxylic dianhydride of (a) is reacted with the aforementioned alcohol and an alcohol having a heterocyclic structure and/or a high heteroatom structure, thereby producing a tetracarboxylic acid (acid/ester) having a heterocyclic structure and/or a high heteroatom structure. Next, by reacting the obtained tetracarboxylic acid (acid/ester) with a catalyst containing the aforementioned divalent organic group Y 1 Amide polycondensation of the diamine to give the polyimide precursor (A) of the present application.
(preparation of acid/ester body)
As a precursor for the preparation of polyimide (A), a polyimide containing tetravalent organic group X is suitably used 1 The tetracarboxylic dianhydride of (2) is preferably a compound represented by the following formula.
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In the above, X 1 Is a group defined in the above general formula (1). The X is 1 More preferably selected from the above general formula (X) 1 -1) and (X) 1 -2) each of the structures shown in the above formula (X) is more preferable 1 -1) the structure shown.
As the tetracarboxylic dianhydride, for example, pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride (alias: oxydiphthalic dianhydride, abbreviated as "ODPA"), benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, abbreviated as "BPDA", diphenylsulfone-3, 3',4,4' -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, and the like. Particular preference is given to pyromellitic anhydride, diphenyl ether-3, 3', 4' -tetracarboxylic dianhydride, benzophenone-3, 3', 4' -tetracarboxylic dianhydride, biphenyl-3, 3', 4' -tetracarboxylic dianhydride, but these are not limited thereto. It goes without saying that they may be used alone or in combination of 2 or more.
As the alcohol having a polymerizable group selected from the group consisting of an acid polymerizable group, a base polymerizable group and a radical polymerizable group which is suitably used for the preparation of the polyimide precursor of (A), for example, 2-hydroxyethyl methacrylate, 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamidoethanol, hydroxymethylvinyl 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-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacryloyloxyethanol, hydroxymethylvinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl acrylate, glycerol, and the like can be cited, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate and the like.
The alcohol having a heterocyclic structure suitable for use in the preparation of the polyimide precursor (a) may be an alcohol having a hydroxyl group and a heterocycle. Examples of the alcohol having a hydroxyl group and a heterocycle include, but are not limited to, N- (2-hydroxyethyl) phthalimide, 3-furanmethanol, 2, 4-dimethyl-6-hydroxypyrimidine, 2-hydroxymethyl-1-methylimidazole, 7-ethyl-3-indoloethanol, hymexazol (5-phenylisoxazol-3-yl) methanol, 3-hydroxyisoxazole-5-carboxylic acid methyl ester, and carragezol (carazol). Among these, the alcohol having a heterocyclic structure is preferably an alcohol having a heterocycle and a (meth) acryloyl group. The compound having a heterocycle and a (meth) acryloyl group can be synthesized from, for example, an epoxy compound and a heterocyclic compound having a nucleophilic functional group typified by a thioether group, a carboxyl group, a hydroxyl group, and the like. The epoxy compound is not limited, and examples thereof include glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether (available from Mitsubishi chemical corporation, for example). Examples of the heterocyclic compound having a nucleophilic functional group include, but are not limited to, 3-mercaptotriazole, 3-mercapto-4-methyl-4H-1, 2, 4-triazole, 5-mercapto-1-methyltetrazole, 5-mercapto-1-phenyltetrazole, 1- (4-hydroxyphenyl) -5-mercapto-1H-tetrazole, 1- (4-carboxyphenyl) -5-mercapto-1H-tetrazole, 1H-tetrazole-5-acetic acid, 5-mercapto-1-methyltetrazole, 1- (4-ethoxyphenyl) -5-mercapto-1H-tetrazole, 4- (1H-tetrazol-5-yl) benzoic acid, 5-mercapto-1- (4-methoxyphenyl) -1H-tetrazole, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 5-benzotriazole carboxylic acid, N-phthaloyl glycine, 1H-benzotriazole-1-methanol, 3-mercapto-1, 2, 4-triazole, 1-methylpyrazole-5-carboxylic acid, 3-methyl-pyrazole-1H-carboxylic acid, 3-methyl-pyrazole-3-4-methyl-pyrazole-carboxylic acid, 3-methyl-pyrazole-4-methyl-4-carboxylic acid, and the like, pyrazole-4-carboxylic acid, 3-carboxyindazole, and the like.
The desired acid/ester can be obtained by stirring the tetracarboxylic dianhydride and the alcohol in a solvent, dissolving and mixing the mixture, and thereby performing an esterification reaction of an acid anhydride group contained in the tetracarboxylic dianhydride. The reaction is preferably carried out in the presence of a suitable basic catalyst such as pyridine. The reaction conditions are not limited, and for example, the reaction is preferably carried out at a temperature of 20℃to 50℃for 4 hours to 10 hours.
(preparation of polyimide precursor)
Under ice-cooling, a proper dehydration condensing agent such as dicyclohexylcarbodiimide is added and mixed to the acid/ester (typically in the form of a solution in a solvent to be described later),1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole, N' -disuccinimidyl carbonate, and the like, thereby enabling the preparation of a polyanhydride from an acid/ester. Dropwise adding a solution containing the polyacid anhydride to a solution containing the divalent organic group Y 1 The diamine of (2) is separately dissolved or dispersed in a solvent, and subjected to amide polycondensation, whereby the objective polyimide precursor can be obtained. In addition, 1-hydroxybenzotriazole and the like may be used depending on the reactivity of the substrate. Alternatively, the acid moiety of the acid/ester is prepared into an acid chloride by using thionyl chloride or the like, and then reacted with a diamine in the presence of a base such as pyridine, whereby the objective polyimide precursor can be obtained.
As containing divalent organic groups Y 1 Preferably a compound of the formula:
H 2 N-Y 1 -NH 2
{ in Y 1 Is a group defined in the above general formula (1). }. The Y is 1 More preferably the above formula (Y) 1 -1) and (Y) 1 -2) the respective illustrated structure.
Further preferable examples of the diamine include p-phenylenediamine, m-phenylenediamine, 4-diaminodiphenyl ether (alias: 4,4' -oxydiphenylamine, abbreviated as "ODA"), 3,4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 3' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, and 3,3' -diaminodiphenyl sulfone, 4' -diaminobiphenyl, 3' -diaminobiphenyl, 4' -diaminobenzophenone, 3' -diaminobenzophenone, 4' -diaminodiphenylmethane 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-aminopropyldimethylsilyl) benzene, o-tolylsulfone, 9-bis (4-aminophenyl) fluorene, and the like; and those wherein a part of hydrogen atoms on the benzene rings are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen or the like, for example, 3 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminodiphenylmethane 2,2 '-dimethyl-4, 4' -diaminodiphenylmethane, 3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dichloro-4, 4' -diaminobiphenyl, and the like, but is not limited thereto. These may be used alone or in combination of 2 or more of them.
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 poor solvent such as water, an aliphatic lower alcohol or a mixed liquid thereof may be added to the obtained polymer component to precipitate the polymer component, and further, the polymer may be purified by repeating the redissolution, reprecipitation precipitation operation or the like, and vacuum drying may be performed, whereby the target polyimide precursor may be isolated. In order to improve the degree of purification, the ionic impurities may be removed by passing a solution of the polymer through a column which is swollen with an appropriate organic solvent and filled with an anion exchange resin or a cation exchange resin or both.
The molecular weight of the polyimide precursor (a) is preferably 8,000 ～ 150,000, more preferably 9,000 to 50,000, when measured as a polystyrene equivalent weight average molecular weight by gel permeation chromatography. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when the weight average molecular weight is 150,000 or less, the dispersibility in a developer is good, and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight average molecular weight was obtained 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.
As the polyimide precursor (a), a non-photosensitive polyimide precursor prepared using only an alcohol having no polymerizable group as described above may be mixed with a photosensitive polyimide precursor. In this case, the blending amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor from the viewpoint of resolution.
(B) Solvent(s)
Examples of the solvent include amides, sulfoxides, urea and derivatives thereof, ketones, esters, lactones, ethers, halogenated hydrocarbons, alcohols, and the like, and specifically, for example, N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, benzene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1, 2-dichloroethane, 1, 4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, and mesitylene. Among them, from the viewpoints of solubility of the resin and stability of the resin composition, 1 or more selected from the group consisting of N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, benzene glycol, and tetrahydrofurfuryl alcohol are preferable.
Among these solvents, a solvent in which the polyimide precursor (a) is completely dissolved is particularly preferable, and is suitably, for example, N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, γ -butyrolactone, or the like. The solvent is more preferably a solvent other than the amide-based solvent. The amide solvent may inhibit the interaction between the substrate and the polymer due to its strong interaction, and thus may reduce the adhesion to the substrate. Therefore, among the above solvents, at least one solvent selected from the group consisting of dimethyl sulfoxide, tetramethylurea and γ -butyrolactone is particularly preferable.
The solvent content in the negative photosensitive resin composition may preferably be 100 parts by mass or more and 1,000 parts by mass or less, 120 parts by mass or more and 700 parts by mass or less, or 125 parts by mass or more and 500 parts by mass or less, based on 100 parts by mass of the polyimide precursor (a).
(C) Photopolymerization initiator
The negative photosensitive resin composition of the present application may further contain (C) a photopolymerization initiator. The photopolymerization initiator is preferably a radical photopolymerization initiator or a photoacid generator.
Examples of the photo radical polymerization initiator include benzophenone compounds such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4' -methyldiphenyl ketone, dibenzyl ketone, fluorenone and the like; acetophenone compounds such as 2,2' -diethoxyacetophenone, 2-hydroxy-2-methylpropenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone compounds such as thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone and diethyl thioxanthone; benzil compounds such as benzil, benzil dimethyl ketal and benzil-beta-methoxyethyl acetal; benzoin compounds such as benzoin and benzoin methyl ether; oxime compounds such as 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (O-benzoyl) oxime, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, and 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime; n-arylglycine compounds such as N-phenylglycine; and peroxides such as benzoyl peroxide, aromatic biimidazole compounds, titanocene compounds, and the like.
(C) The photopolymerization initiator is not limited to the above examples. Among the above photopolymerization initiators, a radical photopolymerization initiator is more preferable, and an oxime compound is more preferable from the viewpoint of light sensitivity.
When the negative photosensitive resin composition contains (C) a photopolymerization initiator, the compounding amount thereof is preferably 0.1 part by mass or more and 20 parts by mass or 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the (a) polyimide precursor. When the amount of the photopolymerization initiator (C) is 0.1 part by mass or more, the photosensitivity or patterning property becomes good, and when it is 20 parts by mass or less, the physical properties of the photosensitive resin layer after curing of the negative-type photosensitive resin composition become good.
(D) Photopolymerizable monomers
In order to improve the resolution of the relief pattern, the negative photosensitive resin composition may optionally contain a monomer (also simply referred to as a "photopolymerizable monomer") having a photopolymerizable unsaturated bond (also simply referred to as a "polymerizable functional group"). The monomer is preferably a (meth) acrylic compound that undergoes radical polymerization by means of a photopolymerization initiator, and is not particularly limited, but examples thereof include ethylene glycol, monoacrylate, diacrylate, monomethacrylate, and dimethacrylate; polyethylene glycol, monoacrylate, diacrylate, monomethacrylate, and dimethacrylate; propylene glycol, monoacrylates, diacrylates, monomethacrylates, and dimethacrylates; polypropylene glycol, monoacrylates, diacrylates, monomethacrylates, and dimethacrylates; glycerol, monoacrylate, diacrylate, triacrylate, monomethacrylate, dimethacrylate and trimethacrylate; cyclohexane, diacrylates and dimethacrylates; 1, 4-butanediol, diacrylates and dimethacrylates; 1, 6-hexanediol, diacrylate and dimethacrylate; neopentyl glycol, diacrylates and dimethacrylates; monoacrylates, diacrylates, monomethacrylates and dimethacrylates of bisphenol a; benzene trimethyl acrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; pentaerythritol, diacrylates, triacrylates, tetraacrylates, dimethacrylates, trimethacrylates and tetramethacrylates; and ethylene oxide adducts or propylene oxide adducts of these compounds.
From the viewpoint of small cure shrinkage upon curing, the photopolymerizable monomer (D) preferably has 2 or more polymerizable functional groups, more preferably 3 or more polymerizable functional groups.
When the negative photosensitive resin composition contains the photopolymerizable unsaturated monomer for improving resolution of the relief pattern, the blending amount of the photopolymerizable unsaturated monomer is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyimide precursor (a).
(E) Thermal alkaline producing agent
The negative photosensitive resin composition may contain (E) a thermal alkaline generator. Thermal alkaline agents refer to compounds that generate a base upon heating. By containing the thermal alkaline generator, imidization of the negative photosensitive resin composition can be further promoted. This can improve the adhesion during low-temperature curing.
The type of the thermal alkaline generator is not particularly limited, and examples thereof include amine compounds protected by t-butoxycarbonyl groups, and thermal alkaline generators shown in patent documents 3 and 4. However, the present invention is not limited to these, and a known thermoalcogenics may be used.
As the amine compound protected by the t-butoxycarbonyl group, examples thereof include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2, 2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1, 3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexane ethanol, and 4- (2-aminoethyl) cyclohexanol, N-methylethanolamine, 3- (methylamino) -1-propanol, 3- (isopropylamino) propanol, N-cyclohexylethanolamine, alpha- [2- (methylamino) ethyl ] benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinmethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4- (3-hydroxyphenyl) piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2- (4-piperidinyl) -2-propanol, 1, 4-butanol bis (3-aminopropyl) ether, 1, 2-bis (2-aminoethoxy) ethane, 2' -oxybis (ethylamine), 1, 14-diamino-3, 6,9, 12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis (3-aminopropyl) ether, 1, 11-diamino-3, 6, 9-trioxaundecane, diethylene glycol bis (3-aminopropyl) ether, and the like; and compounds in which the amino group of the amino acid or its derivative is protected by t-butoxycarbonyl group, but the present invention is not limited to these.
Examples of the thermal alkaline generator compound having a urea structure include, but are not limited to, those described in patent document 4.
When the negative photosensitive resin composition contains (E) the thermal alkali generator, the compounding amount thereof is preferably 0.1 part by mass or more and 40 parts by mass or less, more preferably 0.5 part by mass or more and 30 parts by mass or less, still more preferably 1 part by mass or more and 25 parts by mass or less, and for example, may be 0.5 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of (a) the polyimide precursor. The blending amount is 0.1 part by mass or more from the viewpoint of the imidization promoting effect, and is preferably 30 parts by mass or less from the viewpoint of the physical properties of the cured photosensitive resin layer of the negative photosensitive resin composition.
The negative photosensitive resin composition may further contain components other than the above-mentioned components (a) to (E). The components other than the components (a) to (E) are not limited, and examples thereof include rust inhibitors, hindered phenol compounds, organic titanium compounds, adhesion promoters, sensitizers, thermal inhibitors, and the like.
Rust inhibitor
When a cured film is formed on a substrate made of copper or a copper alloy using a negative photosensitive resin composition, the negative photosensitive resin composition may optionally contain a rust inhibitor in order to suppress discoloration on copper. Examples of the rust inhibitor include an azole compound and a purine compound.
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) benzotriazole, 2- (2-hydroxy-phenyl) benzotriazole, 2 '-hydroxy-2-hydroxy-benzotriazole, 2-hydroxy-phenyl-2' -benzotriazole, 2-hydroxy-methyl-2-hydroxy-benzotriazole, 2-hydroxy-4-hydroxy-benzotriazole, 2-methyl-4-hydroxy-phenyl-benzotriazole, 2-hydroxy-1H-benzotriazole, 2-hydroxy-methyl-benzotriazole, 2-hydroxy-1-hydroxy-benzotriazole, 4-hydroxy-benzotriazole, 2-methyl-hydroxy-1-hydroxy-benzotriazole, 4-hydroxy-phenyl-benzotriazole, 2-hydroxy-phenyl-benzotriazole, and 2-hydroxy-phenyl-benzotriazole can be mentioned, 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.
Particular preference is given to 5-amino-1H-tetrazole, tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. These azole compounds may be used in the form of 1 kind or a mixture of 2 or more kinds.
Specific examples of the purine compounds include, for example, purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2, 6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylamino purine, 1-benzyl adenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) guanine, N- (3-ethylphenyl) guanine, 2-azaadenine, 5-azaadenine, 8-azaguanine, 8-azaxanthine, and derivatives thereof.
When the negative photosensitive resin composition contains the rust inhibitor, the compounding amount thereof is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, still more preferably 0.05 to 5 parts by mass, and for example, may be 0.01 to 5 parts by mass based on 100 parts by mass of the (a) polyimide precursor. When the amount of the rust inhibitor to be blended is 0.01 parts by mass or more based on 100 parts by mass of the polyimide precursor (a), discoloration of the surface of copper or copper alloy can be suppressed when the negative photosensitive resin composition is formed on copper or copper alloy, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent.
Hindered phenol compound
In order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include octadecyl 2, 6-di-tert-butyl-4-methylphenol, 2, 5-di-tert-butylhydroquinone, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 4' -methylenebis (2, 6-di-tert-butylphenol), 4' -thiobis (3-methyl-6-tert-butylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N ' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamide), 2, 4' -butylidenebis (3-methyl-6-tert-butylphenol), pentaerythritol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and pentaerythritol-bis [3, 5-di-tert-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-s-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 is not limited thereto. Of these, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and the like are particularly preferred.
When the negative photosensitive resin composition contains a hindered phenol compound, the compounding amount thereof is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 0.5 part by mass or more and 10 parts by mass or less, 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 a negative photosensitive resin composition is formed on copper or copper alloy, discoloration and corrosion of copper or copper alloy can be prevented, and on the other hand, when 20 parts by mass or less, the photosensitivity is excellent.
Organic titanium compound
The negative photosensitive resin composition may contain an organic titanium compound. By containing the organic titanium compound in the negative photosensitive resin composition, a photosensitive resin layer excellent in chemical resistance can be formed even when curing is performed at a low temperature.
Examples of the usable organic titanium compound include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII):
i) Titanium chelate compound: among them, a titanium chelate compound having 2 or more alkoxy groups is more preferable in view of good storage stability of the negative photosensitive resin composition and good cured pattern. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium di-n-butoxybis (2, 4-pentanedione) diisopropoxide bis (2, 4-pentanedione) titanium, titanium diisopropoxide bis (tetramethylheptanedione) and titanium diisopropoxide bis (ethylacetoacetate).
II) titanium tetraalkoxide compounds: for example, titanium tetra-n-butoxide, titanium tetra-ethoxide, titanium tetra (2-ethylhexoxide), titanium tetra-isobutanooxide, titanium tetra-isopropoxide, titanium tetra-methoxide, titanium tetra-methoxypropanoate, titanium tetra-methylphenoxide, titanium tetra-n-nonanol, titanium tetra-n-propoxide, titanium tetra-stearyl alcohol, titanium tetra [ bis {2,2- (allyloxymethyl) butanol } ], and the like.
III) titanocene compound: for example pentamethylcyclopentadienyl titanium trimethate, bis (. Eta.) 5 -2, 4-cyclopentadienyl-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta. 5 -2, 4-cyclopentadien-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.
IV) titanium monoalkoxide compound: for example, titanium tris (dioctyl phosphoryl) isopropoxide, titanium tris (dodecylbenzenesulfonyl) isopropoxide, and the like.
V) titanium oxide compound: such as bis (pentanedione) titanium oxide, bis (tetramethyl heptanedione) titanium oxide, titanyl phthalocyanine, and the like.
VI) titanium tetra acetylacetonate compound: for example, titanium tetra-acetylacetonate, and the like.
VII) titanate coupling agent: such as isopropyl tri (dodecylbenzenesulfonyl) titanate, and the like.
Among them, the organic titanium compound is preferably at least 1 compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) titanium tetraalkoxide compound and III) titanocene compound from the viewpoint of exhibiting more excellent chemical resistance. Particularly preferred are diisopropoxybis (ethylacetoacetate) titanium, titanium tetra-n-butoxide and bis (. Eta.) 5 -2, 4-cyclopentadienyl-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.
When the negative photosensitive resin composition contains an organic titanium compound, the compounding amount thereof is preferably 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 2 parts by mass or less, relative to 100 parts by mass of the (a) polyimide precursor. When the amount of the compound is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance, while when 10 parts by mass or less, the negative photosensitive resin composition has excellent storage stability.
Bonding aid
In order to improve the adhesion between a film formed using the negative photosensitive resin composition and a substrate, the negative photosensitive resin composition may optionally contain an adhesion promoter. As the adhesion promoter, aluminum-based adhesion promoters, silane coupling agents, and the like can be used.
Examples of the aluminum-based adhesive auxiliary agent include aluminum tris (ethylacetoacetate), aluminum triacetylacetonate, aluminum ethylacetoacetate diisopropoxylate, and the like.
Examples of the silane coupling agent include gamma-aminopropyl dimethoxy silane, N- (. Beta. -aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, gamma-glycidoxypropyl methyl dimethoxy silane, gamma-mercaptopropyl methyl dimethoxy silane, 3-methacryloxypropyl dimethoxy methyl silane, 3-methacryloxypropyl trimethoxy silane, trimethoxyphenyl silane, trimethoxy (p-tolyl) silane, dimethoxymethyl-3-piperidinylpropyl silane, diethoxy-3-glycidoxypropyl methyl silane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl ] phthaloyl acid, benzophenone-3, 3 '-bis (N- [ 3-triethoxysilyl ] propyl amide) -4,4' -dicarboxylic acid, benzene-1, 4-bis (N- [ 3-triethoxysilyl ] propyl amide) -2, 5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, N-phenylaminopropyl trimethoxy silane, 3-ureido propyl trimethoxy silane, 3-triethoxysilyl propyl silane, 3- (triethoxysilyl) propyl succinic anhydride, and (more commercially available from the company); trade name KBM803, CHISSO Co., ltd.: trade name Sila-Ace S810), 3-mercaptopropyl triethoxysilane (AZMAX Co.): trade name SIM 6475.0), 3-mercaptopropyl methyl dimethoxy silane (manufactured by the company of the shin-Etsu chemical industry Co., ltd.: trade name LS1375, manufactured by AZMAX corporation: trade name SIM 6474.0), mercaptomethyltrimethoxysilane (trade name SIM6473.5C manufactured by AZMAX Co., ltd.), mercaptomethyldimethoxysilane (trade name SIM6473.0 manufactured by AZMAX Co., ltd.), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropyloxysilane, 2-mercaptoethylmethoxypropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, N- (3-mercaptoethyldiethoxysilane, 3-trade name: 35 manufactured by AZX, 3-mercaptoethyltriethoxysilane, 3-UK., N- (3-trimethoxysilylpropyl) urea (AZMAX, trade name: SIU 9058.0), N- (3-diethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxypropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-triethoxysilylethyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-tripropylyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by AZMAX Co., ltd.: trade name SLA 0598.0), m-aminophenyltrimethoxysilane (manufactured by AZMAX Co., ltd.: trade name SLA 0599.0), p-aminophenyltrimethoxysilane (manufactured by AZMAX Co., ltd.: SLA 0599.1), aminophenyltrimethoxysilane (manufactured by AZMAX Co., ltd.: SLA 0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by AZMAX Co., ltd.: SIT 8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethyl) pyridine, 2- (diethoxysilylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetran-butoxysilane, tetraisobutoxysilane, tetra-t-butoxysilane, tetra (methoxyethoxysilane), tetra (methoxyn-ethoxysilane), tetra (ethoxyethoxyethoxysilane), tetra (methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, trioxysilyl) trioxysilyl, trioxysilyl Bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl ] disulfide, bis [3- (triethoxysilyl) propyl ] tetrasulfide, di-t-butoxydiacetoxysilane, triethoxysilylaluminum, phenylsilanol, methylphenylsilanol, ethylphenylsilanol, n-propylphenylsilanol, isopropylphenylsilanol, n-butyldiphenylsilanol, isobutylsilanol, t-butylphenylsilanol, diphenylsilanol, dimethoxydiphenylsilanol, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, t-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, t-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, t-butyldiphenylsilanol, and tributyldiphenylsilanol. Further, the silane coupling agents having the structures represented by the following formulas (S-1) are exemplified, but are not limited thereto.
Among these adhesion aids, a silane coupling agent is more preferably used from the viewpoint of adhesion. Among the above silane coupling agents, 1 or more selected from the group consisting of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol and silane coupling agents having structures represented by the respective formulae (S-1) are preferably used from the viewpoint of storage stability.
When the negative photosensitive resin composition contains an adhesion promoter, the amount of the adhesion promoter to be blended is preferably 0.01 parts by mass or more and 25 parts by mass or less, or more preferably 0.5 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the (a) polyimide precursor. The amount of the silane coupling agent to be blended is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the polyimide precursor (a).
Sensitizer
In order to improve the photosensitivity, the negative photosensitive resin composition may optionally contain a sensitizer. As a result of the use of the sensitizer, examples thereof include Michler's ketone, 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-dimethylaminophenylbiphenylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaphtylthiazole, 1, 3-bis (4' -dimethylaminobenzylidene) propanone, 1, 3-bis (4 '-diethylaminobenzylidene) propanone, 3' -carbonyl-bis (7-diethylamino) coumarin, 3-acetyl-7-dimethylamino-7-carbonyl-7-dimethoxycoumarin, 3-dimethoxycarbonyl-7-dimethoxycarbonyl-3-dimethoxycarbonyl-7-dimethoxyethyl-7-2-methoxycarbonyl-7-diethylamino-coumarin, and N-methoxyethyl-7-2-diethylamino-coumarin N-phenyl diethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isopentyl dimethylaminobenzoate, isopentyl 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. They may be used alone or in a combination of, for example, 2 to 5.
When the negative photosensitive resin composition contains a sensitizer for improving photosensitivity, the compounding amount thereof is preferably 0.1 part by mass or more and 25 parts by mass or less relative to 100 parts by mass of the (a) polyimide precursor.
Thermal polymerization inhibitor
In particular, the negative photosensitive resin composition may optionally contain a thermal polymerization inhibitor in order to improve stability of viscosity and photosensitivity when stored in a solution state containing a solvent. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 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-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt, and the like can be used.
< method for producing cured relief Pattern >
The method for manufacturing the solidified relief pattern comprises the following steps:
(1) A step of applying the negative photosensitive resin composition of the present application to a substrate to form a photosensitive resin layer on the substrate (resin layer forming step);
(2) A step of exposing the photosensitive resin layer (exposure step);
(3) Developing the exposed photosensitive resin layer to form a relief pattern (relief pattern forming step); and
(4) And a step of forming a cured relief pattern by performing a heat treatment on the relief pattern (a cured relief pattern forming step).
(1) Resin layer Forming Process
In this step, a negative photosensitive resin composition 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 negative photosensitive resin composition, for example, a method of coating by a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, a method of spray coating by a spray coater, or the like can be used.
The coating film containing the negative photosensitive resin composition may be dried as needed. As a drying method, air drying can be used; oven or hot plate based heat drying; vacuum drying and the like. Specifically, in the case of air-drying or heat-drying, the drying may be performed at 20 to 150 ℃ for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on a substrate.
(2) Exposure process
In this step, the photosensitive resin layer formed as described above is exposed to light through a photomask or a photomask having a pattern or directly using an ultraviolet light source or the like by using an exposure device such as a contact aligner, a mirror projector, or a stepper. By this exposure, the polymerizable group of the (a) polyimide precursor contained in the negative photosensitive resin composition is crosslinked by the action of the (C) photopolymerization initiator. By this crosslinking, the exposed portion is insoluble in a developer described later, and thus a relief pattern can be formed.
Thereafter, for the purpose of improving the photosensitivity or the like, post-exposure baking (PEB) or pre-development baking or both may be performed based on an arbitrary combination of temperature and time as needed. The baking conditions are preferably: the temperature is 40 to 120 ℃ and the time is 10 to 240 seconds, and the range is not limited as long as the properties of the negative photosensitive resin composition of the present application are not impaired.
(3) Relief pattern forming step
In this step, 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 may be selected from conventionally known developing methods for photoresists, for example, a spin spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. After development, for the purpose of adjusting the shape of the relief pattern or the like, post-development baking may be performed based on any combination of temperature and time as needed.
The developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition or a combination of the good solvent and a poor solvent. The good solvent is preferably, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, cyclopentanone, cyclohexanone, gamma-butyrolactone, alpha-acetyl-gamma-butyrolactone, or the like. As the lean solvent, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable, for example. When the poor solvent and the poor solvent are mixed and used, 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. The solvent may be used in combination of 2 or more, for example, a plurality of solvents.
(4) Curing relief pattern formation process
In this step, the relief pattern obtained by the development is subjected to a heat treatment to volatilize the photosensitive component, and the polyimide precursor (a) is imidized to convert the cured relief pattern formed of polyimide. As the heat treatment method, various methods such as a method using a heating 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 heat treatment may be performed at 160℃to 350℃for 30 minutes to 5 hours, for example. The temperature of the heat treatment is preferably 200℃or lower, more preferably 180℃or lower. 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.
The photosensitive resin layer after exposure has a crosslinked structure formed by crosslinking the polymerizable groups of the polyimide precursor (a). But can be considered as: the crosslinked structure is released from the polymer upon heating in the step of forming a cured relief pattern, and the amic acid structure formed by the release is closed to form an imide ring structure, thereby obtaining a cured relief pattern formed of polyimide.
< polyimide cured film >
The present application also provides a cured film formed from the negative photosensitive resin composition of the present application. It can be considered that: the cured film formed from the negative photosensitive resin composition contains polyimide having a structure represented by the following general formula (4).
In the general formula (4), X 1 And Y 1 Respectively with X in the general formula (1) 1 And Y 1 The same applies. For the same reason, X in the general formula (1) is preferable 1 、Y 1 Among the polyimides of the general formula (4), polyimide is also preferable.
< semiconductor device >
The present application also provides a semiconductor device having a cured relief pattern obtained from the negative photosensitive resin composition. Specifically, provided is a semiconductor device having a substrate as a semiconductor element and a cured relief pattern. The cured relief pattern can be produced by the method for producing the cured relief pattern using the negative photosensitive resin composition.
The present application also provides a method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the method for manufacturing a cured relief pattern according to the present embodiment as a part of the steps. In this case, the cured relief pattern formed by the method for manufacturing a cured relief pattern according to the present application can be 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 of a semiconductor device, and can be manufactured in combination with a known method for manufacturing a semiconductor device.
< display device >
The present application also provides a display device 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. The cured film can be applied to, for example, surface protective films, insulating films, planarizing films, and the like of TFT liquid crystal display elements and color filter elements; protrusions for MVA type liquid crystal display devices; partition walls for organic EL element cathodes, and the like.
The negative photosensitive resin composition of the present application is useful for applications such as interlayer insulation of a multilayer circuit, coverlay coating of a flexible copper clad laminate, solder resist, and liquid crystal alignment film, in addition to the application to the above-described semiconductor device.
Example 1
Hereinafter, embodiments of the present application will be specifically described by way of examples, but the present application is not limited thereto. In examples, comparative examples and production examples, physical properties of a polyimide precursor or a negative photosensitive resin composition were measured and evaluated in accordance with the following methods.
< measurement conditions >
(1) Weight average molecular weight
The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion) under the following conditions.
And (3) a pump: JASCO PU-980
A detector: JASCO RI-930
Column oven: JASCO CO-965 at 40deg.C
Column: shodex KD-805/KD-804/KD-803 series manufactured by Shodex electric company
Standard monodisperse polystyrene: shodex STANDARD SM-105 manufactured by Showa electric company
Mobile phase: 0.1 mol/LLiBr/N-methyl-2-pyrrolidone (NMP)
Flow rate: 1mL/min.
(2) Preparation of cured film on Cu
Ti having a thickness of 200nm and Cu having a thickness of 400nm were sequentially sputtered on a 6-inch silicon wafer (manufactured by Fujimi electronics industry Co., ltd., thickness of 625.+ -. 25 μm) using a sputtering apparatus (manufactured by CANON ANELVA Co., ltd.). Next, a negative photosensitive resin composition prepared by a method described later was Spin-coated on the wafer using a Coater Developer (D-Spin 60A type, manufactured by SOKUDO Co.), and pre-baked at 110℃for 180 seconds with a heating plate to form a coating film. The obtained coating film was subjected to a heating treatment for 2 hours under a nitrogen atmosphere at the temperature shown in tables 2 and 3 using a temperature-programmed curing oven (model VF-2000, manufactured by KOYO LINDBERG Co.), whereby a cured film of a resin having a thickness of about 10 μm was obtained on Cu.
(3) Copper adhesion evaluation
The cured film obtained by treating the negative photosensitive resin composition prepared by the method described below was subjected to the above method, and the adhesion characteristics between the copper substrate and the cured resin coating film were evaluated according to the following criteria, in accordance with the transverse cutting method of JIS K5600-5-6.
A: the number of lattices of the cured resin coating film adhered to the substrate is 80 to 100 inclusive
B: the number of lattices of the cured resin coating film adhered to the substrate is 60 or more and less than 80
C: the number of lattices of the cured resin coating film adhered to the substrate is 40 or more and less than 60
D: the number of lattices of the cured resin coating film adhered to the substrate is less than 40
(4) Evaluation of residual film Rate after curing
The film residue ratio of the cured film obtained in (2) was calculated according to the following definition.
Film residue after curing [% ] = (film thickness after curing [ μm ]) x 100 film residue obtained by the above formula was evaluated according to the following criteria.
AA: the residual film rate after curing is more than 93 percent
A: the residual film rate after curing is more than 90% and less than 93%
B: the residual film rate after curing is more than 85 percent and less than 90 percent
C: the residual film rate after curing is more than 80 percent and less than 85 percent
The film thickness after curing and the film thickness before curing were measured using a stylus type contour machine tool (trade name "P-17").
(5) Determination of imidization Rate
The cured relief pattern resin portion was measured by an ATR-FTIR measuring device (manufactured by Nicolet Continuum, thermo Fisher Scientific Co.) using a Si prism, and 1380cm was calculated -1 The peak intensity divided by 1500cm -1 The imidization index obtained by dividing the imidization index of the films obtained by curing the resin composition at 350℃was calculated as the imidization index of the films of each of the examples and comparative examples. The imidization ratio was evaluated based on the following criteria.
A: imidization ratio of 95% or more
B: the imidization ratio is 90% or more and less than 95%
C: imidization rate is 80% or more and less than 90%
D: imidization rate is less than 80%
Synthesis example 1
(Synthesis of heterocyclic Compound 1)
8.81g (0.062 m.cndot.l) of Glycidyl Methacrylate (GMA) and 30.0g of gamma-butyrolactone and 0.63g (0.006 m.cndot.l) of Triethylamine (TEA) were put into a 100mL three-necked flask, and 6.27g (0.062 m.cndot.l) of 3-mercaptotriazole was added dropwise thereto and stirred overnight, thereby obtaining a gamma-butyrolactone solution of heterocyclic compound 1. The heterocyclic compound 1 is a compound shown below. Regarding the heteroatom ratio of the heterocyclic compound 1, since the number of atoms other than the hydrogen atom among the constituent atoms is respectively N atom 3, S atom 1, O atom 3, and C atom 9, it is calculated as { (3+1+3)/(3+1+3+9) } ×100=44%. The "heteroatom ratio of side chain compound" is shown in table 1. The same applies to other side chain compounds.
(Synthesis of Polymer A-1 as a polyimide precursor (A))
31.0g (0.1 mol) of 4,4' -Oxydiphthalic Dianhydride (ODPA) was charged into a 1L-capacity separable flask, and 40.0g of gamma-butyrolactone was added. Then, 50.9g (heterocyclic compound 1:0.062 m/. Mu.l) of a gamma-butyrolactone solution of heterocyclic compound 1 and 19.0g (HEMA, 0.15 m/. Mu.l) of 2-hydroxyethyl methacrylate were charged, and 15.8g of pyridine was added thereto while stirring, followed by stirring at room temperature overnight.
Subsequently, 30.0g (0.20 m.sup.l) of 1-hydroxybenzooxazole (HOBt) was added while stirring the obtained reaction mixture, and then a solution obtained by dissolving 40.4g (0.20 m.sup.l) of Dicyclohexylcarbodiimide (DCC) in 40.0g of gamma-butyrolactone was added under ice-cooling for 20 minutes, and then a suspension obtained by suspending 35.2g (0.09 m.sup.l) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (hereinafter referred to as BAPP) in 35.0g of gamma-butyrolactone was added for 20 minutes. After stirring at room temperature for 4 hours, 18g of ethanol was added, followed by stirring for 1 hour, and then 140g of γ -butyrolactone was added. The reaction mixture is filtered, and the precipitate generated in the reaction system is removed, so as to obtain a reaction liquid.
The obtained reaction solution was added to 1.2kg of ethanol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 300g of gamma-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 2.0kg of water to reprecipitate the polymer. The obtained reprecipitate was collected by filtration and then dried in vacuo, whereby a polymer (polymer A-1) was obtained as a powder. As a result of measuring the molecular weight of the polymer A-1 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 15,000.
Synthesis example 2
(Synthesis of Polymer A-2 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 1 except that 50.9g of the gamma-butyrolactone solution of the heterocyclic compound 1 of Synthesis example 1 was changed to 17.0g (heterocyclic compound 1:0.021 m. Mu.l) and 19.0g of HEMA was changed to 24.4g, thereby obtaining a polymer A-2. As a result of measuring the molecular weight of the polymer A-2 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 23,000.
< synthetic example 3>
(Synthesis of Polymer A-3 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 1 except that 21.8g (0.1 m/l) of pyromellitic anhydride (PMDA) was used in place of 31.0g of 4,4' -Oxydiphthalic Dianhydride (ODPA) in Synthesis example 1, to obtain a polymer A-3. As a result of measuring the molecular weight of the polymer A-3 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 16,000.
< synthetic example 4>
(Synthesis of Polymer A-4 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 1 except that 29.4g (0.1 m.o.l) of 4-4 '-biphenyldicarboxylic anhydride (hereinafter referred to as BPDA) was used in place of 31.0g of 4,4' -Oxydiphthalic Dianhydride (ODPA) in Synthesis example 1, to obtain Polymer A-4. As a result of measuring the molecular weight of the polymer A-4 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 15,000.
Synthesis example 5
(Synthesis of Polymer A-5 as a polyimide precursor (A))
The reaction was carried out in the same manner as in Synthesis example 1 except that 52.0g (0.1 mKl) of 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (hereinafter referred to as BisDA) was used in place of 31.0g of 4,4' -Oxydiphthalic Dianhydride (ODPA) in Synthesis example 1, to obtain polymer A-5. As a result of measuring the molecular weight of the polymer A-5 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 18,000.
< synthetic example 6>
(Synthesis of Polymer A-6 as a polyimide precursor (A))
The reaction was carried out in the same manner as in Synthesis example 1 except that 17.2g (0.083 m. Mu.l) of 4, 4-diaminodiphenyl ether was used in place of 35.2g of BAPP in Synthesis example 1, to thereby obtain a polymer A-6. As a result of measuring the molecular weight of the polymer A-6 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 17,000.
< synthetic example 7>
(Synthesis of Polymer A-7 as a polyimide precursor (A))
The reaction was carried out in the same manner as in Synthesis example 1 except that 17.7g (0.083 m. Mu.l) of m-toluidine was used in place of 35.2g of BAPP in Synthesis example 1, to thereby obtain a polymer A-7. As a result of measuring the molecular weight of the polymer A-7 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 17,000.
Synthesis example 8
(Synthesis of Polymer A-8 as a polyimide precursor (A))
The reaction was carried out in the same manner as in Synthesis example 1 except that 9.0g (0.083 mL) of p-phenylenediamine was used in place of 35.2g of BAPP in Synthesis example 1, to thereby obtain a polymer A-8. As a result of measuring the molecular weight of the polymer A-8 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 18,000.
< synthetic example 9>
(Synthesis of heterocyclic Compound 2)
To a 100mL three-necked flask, 8.81g of GMA and 30.0g of gamma-butyrolactone and 0.63g of Triethylamine (TEA) were charged 7.20g of 5-mercapto-1-methyltetrazole, and the mixture was stirred overnight, thereby obtaining a gamma-butyrolactone solution of heterocyclic compound 2. The heterocyclic compound 2 is a compound shown below.
(Synthesis of Polymer A-9 as a polyimide precursor (A))
The reaction was carried out in the same manner as in the above-described synthesis example 1 except that 51.8g of the gamma-butyrolactone solution of the heterocyclic compound 2 was used instead of 50.9g of the gamma-butyrolactone solution of the heterocyclic compound 1 of synthesis example 1 and HOBt was changed to 0g (not used), thereby obtaining a polymer a-9. As a result of measuring the molecular weight of the polymer A-9 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.
< synthetic example 10>
(Synthesis of Polymer A-10 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 9 except that 50.9g of the gamma-butyrolactone solution of the heterocyclic compound 2 of Synthesis example 9 was changed to 17.3g (heterocyclic compound 2:0.021 m. Mu.l) and 19.0g of HEMA19.4 g was changed to 24.4g, whereby a polymer A-10 was obtained. As a result of measuring the molecular weight of the polymer A-10 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 22,000.
Synthesis example 11
(Synthesis of Polymer A-11 as a polyimide precursor (A))
The reaction was carried out in the same manner as in Synthesis example 1 except that 50.9g (heterocyclic compound 1:0.062 m. Mu.l) of the gamma-butyrolactone solution of the heterocyclic compound 1 of Synthesis example 1 was changed to 11.9g (0.062 m. Mu.l) of N- (2-hydroxyethyl) phthalimide (NHPA, indicated as "heterocyclic compound 3" in the table), and 30.0g (HOBt) was changed to 0g (not used), to obtain Polymer A-11. As a result of measuring the molecular weight of the polymer A-11 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 18,000.
Synthesis example 12
(Synthesis of Polymer A-12 as a polyimide precursor (A))
The reaction was carried out in the same manner as in Synthesis example 1 except that 50.9g (heterocyclic compound 1:0.062 m.l) of the gamma-butyrolactone solution of the heterocyclic compound 1 of Synthesis example 1 was changed to 4.00g (0.021 m.l) of N- (2-hydroxyethyl) phthalimide (NHPA), 24.4g of HEMA19.0g was changed to 30.0g of HOBt (not used), and the reaction was carried out to obtain a polymer A-12. As a result of measuring the molecular weight of the polymer A-12 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.
< synthetic example 13>
(Synthesis of Polymer A-13 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 1 except that 50.9g (heterocyclic compound 1:0.062m /) of the gamma-butyrolactone solution of the heterocyclic compound 1 of Synthesis example 1 was changed to 6.08g (0.062 m /) of 3-furanmethanol (referred to as "heterocyclic compound 4" in the table), and 30.0g (not used) of HOBt was changed to 0g, to give a polymer A-13. As a result of measuring the molecular weight of the polymer A-13 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 23,000.
Synthesis example 14
(Synthesis of Polymer A-14 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 1 except that 50.9g (heterocyclic compound 1:0.062m /) of the gamma-butyrolactone solution of the heterocyclic compound 1 of Synthesis example 1 was changed to 7.70g (0.062 m /) of 2, 4-dimethyl-6-hydroxypyrimidine (referred to as "heterocyclic compound 5" in the table), and 30.0g (HOBt) was changed to 0g (not used), to give Polymer A-14. As a result of measuring the molecular weight of the polymer A-14 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 15,000.
< synthetic example 15>
(Synthesis of Polymer A-15 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 1 except that 50.9g (heterocyclic compound 1:0.062 m.l) of the gamma-butyrolactone solution of the heterocyclic compound 1 of Synthesis example 1 was changed to 6.95g (0.062 m.l) of 2-hydroxymethyl-1-methylimidazole (referred to as "heterocyclic compound 6" in the table), and 30.0g of HOBt was changed to 0g (not used), to give Polymer A-15. As a result of measuring the molecular weight of the polymer A-15 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 24,000.
Synthesis example 16
(Synthesis of Polymer A-16 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 1 except that 50.9g (heterocyclic compound 1:0.062 m. Mu.l) of the gamma-butyrolactone solution of the heterocyclic compound 1 of Synthesis example 1 was changed to 11.7g (0.062 m. Mu.l) of 7-ethyl-3-indolylethanol (referred to as "heterocyclic compound 7" in the table), and 30.0g of HOBt was changed to 0g (not used), to give Polymer A-16. As a result of measuring the molecular weight of the polymer A-16 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 22,000.
< synthetic example 17>
(Synthesis of Polymer A-17 as a polyimide precursor (A))
ODPA 31.0g (0.1 mol) was charged into a 1L capacity separable flask, and 40.0g of gamma-butyrolactone was added. Subsequently, 26.5g of HEMA was charged, 15.8g of pyridine was added thereto with stirring, and the mixture was stirred at 40℃for 4 hours using an oil bath to obtain a reaction mixture. After the reaction was completed, the mixture was naturally cooled to room temperature and left for 16 hours.
Then, while stirring the obtained reaction mixture, a solution obtained by dissolving 40.4g of DCC in 40g of γ -butyrolactone was added under ice-cooling for 40 minutes, and then a suspension obtained by suspending 35.2g (0.086 m g/l) of bapp in 35.0g of γ -butyrolactone was added for 20 minutes. After stirring at room temperature for 4 hours, 9.0g of ethanol was added, followed by stirring for 1 hour, and then 140g of γ -butyrolactone was added. The reaction mixture is filtered, and the precipitate generated in the reaction system is removed, so as to obtain a reaction liquid.
The resulting reaction solution was added to 600g of ethanol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 300g of gamma-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 1kg of water to reprecipitate the polymer. The obtained reprecipitate was collected by filtration and then dried in vacuo, whereby a polymer (polymer A-17) was obtained as a powder. As a result of measuring the molecular weight of Polymer A-17 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 25000.
Synthesis example 18 ]
(Synthesis of Polymer A-18 as a polyimide precursor (A))
The reaction was carried out in the same manner as in Synthesis example 1 except that 35.2g (0.09 mL) of BAPP was changed to 22.3g (0.09 mL) of bis (3-aminophenyl) sulfone, and the reaction was carried out to obtain a polymer A-18. As a result of measuring the molecular weight of Polymer A-18 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 19,000.
Synthesis example 19 ]
(Synthesis of Urea Compound 1)
10.5g of 1-Aminoethoxyethanol (AEE) and 26.0g of gamma-butyrolactone were charged into a 100mL three-necked flask, and cooled to 0 ℃. To this was added dropwise 15.5g of Karenz M OI (trade name; showa electric company) to obtain a gamma-butyrolactone solution of urea compound 1. Urea compound 1 is a compound shown below.
(Synthesis of Polymer A-19 as a polyimide precursor (A))
31.0g (0.1 mol) of 4,4' -Oxydiphthalic Dianhydride (ODPA) was charged into a 1L-capacity separable flask, and 37.5g of gamma-butyrolactone was added. Then, 32.2g of a gamma-butyrolactone solution of urea compound 1 (urea compound 1:0.062 m. Mu.l) and 18.2g of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA, 0.14 m. Mu.l) were charged, 15.8g of pyridine was added while stirring, and then, the mixture was stirred at 40℃for 5 hours using an oil bath to obtain a reaction mixture. After the reaction was completed, the mixture was naturally cooled to room temperature and left for 16 hours.
Then, while stirring the obtained reaction mixture, a solution obtained by dissolving 40.7g of Dicyclohexylcarbodiimide (DCC) in 50g of γ -butyrolactone was added under ice-cooling for 40 minutes, and then a suspension obtained by suspending 35.2g (0.086 m /) of BAPP in 150g of γ -butyrolactone was added for 60 minutes. After stirring at room temperature for 2 hours, 9.0g of ethanol was added, followed by stirring for 1 hour, and then 70g of γ -butyrolactone was added. The reaction mixture is filtered, and the precipitate generated in the reaction system is removed, so as to obtain a reaction liquid.
The obtained reaction solution was added to 1.2kg of ethanol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 300g of gamma-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 3.5kg of water to reprecipitate the polymer. The obtained reprecipitate was collected by filtration and then dried in vacuo, whereby a polymer (polymer A-19) was obtained as a powder. As a result of measuring the molecular weight of Polymer A-19 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 29000.
< synthetic example 20>
(Synthesis of Polymer A-20 as a polyimide precursor (A))
A reaction was carried out in the same manner as in Synthesis example 1 except that 50.9g of the gamma-butyrolactone solution of the heterocyclic compound 1 of Synthesis example 1 was changed to 10.80g of 1- (4-aminobenzyl) -1,2, 4-triazole (heterocyclic compound 1: 0.062. Mu.l), and a polymer A-20 was obtained. As a result of measuring the molecular weight of Polymer A-20 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 14,000.
Example 1 ]
Using the polyimide precursor a-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. A-1 to be a polyimide precursor of (a): 100g of the polymer was dissolved in 100g of gamma-butyrolactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of GBL, to prepare a negative photosensitive resin composition. The composition was evaluated as described above.
Example 2 ]
Using the polyimide precursor a-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. A-1 to be a polyimide precursor of (a): 100g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) -oxime (hereinafter referred to as PDO, C-1) as a photopolymerization initiator (C) 3g was dissolved in 100g of gamma-butyrolactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of GBL, to prepare a negative photosensitive resin composition. The composition was evaluated as described above.
Example 3 ]
Using the polyimide precursor a-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. A-1 to be a polyimide precursor of (a): 100g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) -oxime (hereinafter referred to as PDO, C-1) as a photopolymerization initiator (C), 3g of pentaerythritol tetraacrylate (New Zhongcun chemical Co., A-TMMT) as a polymerizable monomer (D), 20g (D-1) was dissolved in 100g of gamma-butyrolactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of GBL, to prepare a negative photosensitive resin composition. The composition was evaluated as described above.
< examples 4 to 23, comparative examples 1 to 5>
Negative photosensitive resin compositions similar to those in examples 1 to 3 were prepared using the polymers, photoinitiators, polymerizable monomers, and solvents shown in tables 2 and 3, and evaluated by the methods described above.
Example 24 ]
Using the polyimide precursor a-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. A-1 to be a polyimide precursor of (a): 100g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) -oxime (hereinafter referred to as PDO, C-1) as a photopolymerization initiator (C), 3g of pentaerythritol tetraacrylate (D-1) as a polymerizable monomer (D), 20g of (E-1) as a thermal alkaline generator (E) and 100g of gamma-butyrolactone (hereinafter referred to as GBL) were dissolved. The viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of GBL, to prepare a negative photosensitive resin composition. The composition was evaluated as described above.
TABLE 1
Table 1.
TABLE 2
TABLE 3
TABLE 3 Table 3
C-1: 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) -oxime (PDO)
D-1: pentaerythritol tetraacrylate
D-2: methacrylic acid 2-hydroxy ethyl ester
D-3: tricyclodecane dimethanol diacrylate (New Zhongcun chemical industry Co., A-DCP)
D-4: dipentaerythritol polyacrylate (Xinzhongcun chemical industry Co., ltd., A-DPH)
E-1: a compound represented by the following formula.
Industrial applicability
By using the negative photosensitive resin composition of the present application, a cured relief pattern having high copper adhesion and less film shrinkage in the heating step after heat curing can be obtained. The negative photosensitive resin composition of the present application can be suitably used in the field of photosensitive materials useful for the production of electric/electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (19)

1. A negative photosensitive resin composition comprising:
(A) A polyimide precursor comprising a structural unit represented by the following general formula (1); and
(B) The solvent is used for the preparation of the aqueous solution,
in the formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a hetero atom, and a monovalent organic group having a heterocyclic structure, wherein R 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure.
2. A negative photosensitive resin composition comprising:
(A) A polyimide precursor comprising a structural unit represented by the following general formula (1); and
(B) The solvent is used for the preparation of the aqueous solution,
in the formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure, wherein OR 1 And OR 2 At least one of the groups is a monovalent organic group having a proportion of hetero atoms other than hydrogen atoms of 42% or more.
3. The negative-type photosensitive resin composition according to claim 1 or 2, further comprising (C) a photopolymerization initiator.
4. The negative-type photosensitive resin composition according to claim 1 or 2, wherein R 1 And R is 2 At least one of them is a monovalent organic group comprising a heterocyclic structure comprising a nitrogen atom.
5. The negative-type photosensitive resin composition according to claim 1 or 2, wherein R 1 And R is 2 At least one of them is a heterocyclic ring structure containing five-membered ringsA monovalent organic group, and the five-membered ring heterocyclic structure contains a nitrogen atom.
6. The negative-type photosensitive resin composition according to claim 1 or 2, wherein R is in all structural units of the (a) polyimide precursor 1 And R is 2 At least one of them has a (meth) acrylate group.
7. The negative-type photosensitive resin composition according to claim 1 or 2, wherein R is in all structural units of the (a) polyimide precursor 1 And R is 2 The total of two or more (meth) acrylate groups.
8. The negative-type photosensitive resin composition according to claim 1 or 2, wherein R 1 And R is 2 At least one of them is a group represented by the following general formula (3),
in the formula (3), ar is the heterocyclic structure; the dotted line is a single bond to the oxygen atom of formula (1); r is R 3 、R 4 And R is 5 Each independently is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; r is R 6 And R is 7 Each independently is a divalent organic group having 1 to 10 carbon atoms optionally containing a heteroatom.
9. The negative-type photosensitive resin composition according to claim 1 or 2, wherein R 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure, which is triazole or tetrazole.
10. The negative-type photosensitive resin composition according to claim 1 or 2, wherein R in the (a) polyimide precursor 1 And R is 2 More than 10 mole% of the whole has the heterocyclic structureAnd/or a structure in which the proportion of the number of hetero atoms is high.
11. The negative photosensitive resin composition according to claim 1 or 2, further comprising (D) a monomer having a polymerizable functional group.
12. The negative-working photosensitive resin composition according to claim 1 or 2, wherein the (D) polymerizable functional group-containing monomer has 2 or more polymerizable functional groups.
13. The negative-working photosensitive resin composition according to claim 1 or 2, wherein the (D) polymerizable functional group-containing monomer has 3 or more polymerizable functional groups.
14. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the X 1 Comprising at least 1 selected from the group consisting of the following general formulae (8) to (11),
15. the negative-type photosensitive resin composition according to claim 1 or 2, wherein the Y 1 Comprising at least 1 selected from the group consisting of the following general formulae (12) to (15),
wherein R is 11 Each independently is a monovalent organic group having 1 to 10 carbon atoms optionally containing a halogen atom; a is an integer of 0 to 4.
16. The negative photosensitive resin composition according to claim 1 or 2, further comprising 0.1 parts by mass or more and 40 parts by mass or less of (E) a thermal alkali generator relative to 100 parts by mass of the (a) polyimide precursor.
17. A method of manufacturing a cured relief pattern comprising the steps of:
(1) A step of applying the negative photosensitive resin composition according to claim 1 or 2 to a substrate to form a photosensitive resin layer on the substrate;
(2) Exposing the photosensitive resin layer;
(3) Developing the exposed photosensitive resin layer to form a relief pattern; and
(4) And a step of heating the relief pattern to form a cured relief pattern.
18. A polyimide precursor comprising a structural unit represented by the following general formula (1),
in the formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure, wherein R 1 And R is 2 At least one of them is a monovalent organic group having a heterocyclic structure.
19. A polyimide precursor comprising a structural unit represented by the following general formula (1),
in the formula (1), X 1 A tetravalent organic group having 4 to 40 carbon atoms which optionally contains a hetero atom; y is Y 1 Is a divalent organic group having 6 to 40 carbon atoms optionally containing a heteroatom; r is R 1 And R is 2 Each independently is 1 selected from the group consisting of a hydrogen atom, a monovalent organic group having 1 to 40 carbon atoms optionally containing a heteroatom, and a monovalent organic group having a heterocyclic structure, wherein OR 1 And OR 2 At least one of the groups is a monovalent organic group having a proportion of hetero atoms other than hydrogen atoms of 42% or more.
CN202310124490.5A 2022-02-17 2023-02-16 Polyimide precursor, negative photosensitive resin composition, and method for producing cured relief pattern using same Pending CN116609998A (en)

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