CN117055288A - Negative photosensitive polyimide composition, method for producing pattern, and electronic component - Google Patents

Negative photosensitive polyimide composition, method for producing pattern, and electronic component Download PDF

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Publication number
CN117055288A
CN117055288A CN202210491940.XA CN202210491940A CN117055288A CN 117055288 A CN117055288 A CN 117055288A CN 202210491940 A CN202210491940 A CN 202210491940A CN 117055288 A CN117055288 A CN 117055288A
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group
formula
component
parts
negative photosensitive
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Inventor
刘斌
向文胜
刘亦杰
张兵
赵建龙
鲍杰
季学华
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Jiangsu Aisen Semiconductor Material Co ltd
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Jiangsu Aisen Semiconductor Material Co ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70008—Production of exposure light, i.e. light sources

Abstract

The present invention provides a negative photosensitive polyimide composition, a method for producing a pattern, and an electronic component, wherein the negative photosensitive polyimide composition contains the following components (a), (b), (c), and (d): (a) a polymer soluble in an aqueous alkaline solution, (b) a photopolymerization initiator, (c) a compound having a polymerizable functional group including an unsaturated double bond or triple bond, and (d) a thermal crosslinking agent. The negative photosensitive polyimide composition of the present invention is easily soluble in an alkaline aqueous solution at a portion not exposed to ultraviolet light, and is insoluble in an alkaline aqueous solution at a portion exposed to ultraviolet light, thus being capable of effectively reproducing a fine pattern. The negative photosensitive polyimide composition of the present invention has an excellent dissolution rate ratio (contrast) between the unexposed portion and the exposed portion, and has excellent resolution, adhesion, chemical resistance, and storage stability.

Description

Negative photosensitive polyimide composition, method for producing pattern, and electronic component
Technical Field
The invention belongs to the technical field of photosensitive resin, and relates to a negative photosensitive polyimide composition, a method for manufacturing a pattern, a cured product, an interlayer insulating film, a surface protection film and an electronic component. More specifically, the present invention relates to a negative photosensitive polyimide composition which can be developed with an alkaline aqueous solution without decreasing sensitivity and maintaining a good pattern shape with excellent resolution, a method for producing a pattern cured film using the composition, and an electronic component.
Background
Conventionally, polyimide resins having excellent heat stability, electrical insulation and mechanical properties have been generally used for surface protective films and interlayer insulating films of semiconductor devices. Such a polyimide resin film is generally formed by applying a polyimide precursor (polyamic acid) solution obtained by polycondensation of tetracarboxylic dianhydride and diamine in a polar solvent, forming a film by spin coating or the like, and then dehydrating and ring-closing curing by heating (see non-patent document 1).
In recent years, photosensitive polyimide has a photosensitive characteristic, and thus has a feature of simplifying a patterning process and shortening a complicated patterning process, and has been widely used for a surface protective film, an interlayer insulating film, and the like in the fields of semiconductor devices and integrated circuit packages (see patent documents 1 to 3).
Conventionally, organic solvents such as N-methylpyrrolidone have been used for developing the photosensitive polyimide. However, in recent years, development with an alkali aqueous solution is considered to be less problematic due to environmental awareness and in view of treatment of waste liquid, but these photosensitive polyimide materials are poor in solubility and difficult to form patterns (see patent documents 4 to 5). In addition, a negative photosensitive polyimide material that can be used for alkali aqueous solution development must contain alkali-soluble groups, but it is difficult to effectively reproduce a pattern after development of such a material (see non-patent document 2). With the demand for power consumption of semiconductor devices, polybenzoxazole materials are receiving attention due to their lower dielectric constant and lower water absorption. However, materials having both negativity and excellent alkaline developability have not been reported yet.
Accordingly, in the art, development of a photosensitive polyimide composition having both of negativity and excellent alkali developability has been desired.
Patent document 1: japanese patent laid-open No. 49-115541.
Patent document 2: japanese patent laid-open No. 59-108031.
Patent document 3: japanese patent laid-open No. 59-219330.
Patent document 4: japanese patent laid-open No. 54-109828.
Patent document 5: japanese patent laid-open No. 11-24268.
Non-patent document 1: polyimide-structure, properties and applications.
Non-patent document 2: journal of Photopolymer Science and Technology,1997,10 (1), 55-60.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a negative photosensitive polyimide composition, a method for manufacturing a pattern, and an electronic component. The present invention provides a negative photosensitive polyimide composition soluble in an alkaline aqueous solution having a specific structure, wherein a portion of the negative photosensitive polyimide composition not exposed to ultraviolet light is easily soluble in the alkaline aqueous solution, and a portion exposed to ultraviolet light is not soluble in the alkaline aqueous solution, thereby enabling to effectively reproduce a fine pattern.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a negative photosensitive polyimide composition containing the following components (a), (b), (c) and (d):
(a) A polymer soluble in an aqueous alkaline solution;
(b) A photopolymerization initiator;
(c) A compound having a polymerizable functional group including an unsaturated double bond or a triple bond;
(d) A thermal crosslinking agent.
In the present invention, the negative photosensitive polyimide composition contains both components (a), (b), (c) and (d), which have negative characteristics, are developable with an alkaline aqueous solution, and the portion of the negative photosensitive polyimide composition that is not exposed to ultraviolet light is easily soluble in the alkaline aqueous solution, while the portion exposed to ultraviolet light is insoluble in the alkaline aqueous solution, thus being capable of effectively reproducing fine patterns. The negative photosensitive polyimide composition of the present invention has an excellent dissolution rate ratio (contrast) between the unexposed portion and the exposed portion, and has excellent resolution, adhesion, chemical resistance, and storage stability.
Preferably, the component (a) has a structural unit represented by formula 1,
wherein R is selected from hydrogen, CH, identically or differently for each occurrence 2 ＝CH-COOCH 2 CH 2 -or CH 2 ＝C(CH 3 )-COOCH 2 CH 2 -any one of the following; u is a 4-valent organic group, V is a 2-valent organic group, and W is a 3-valent organic group.
Preferably, W is selected, identically or differently, at each occurrence, from any one of the 3-valent organic groups represented by formula 2:
wherein R is 1 -R 3 Are monovalent organic groups, and are each independently selected from any one of hydrogen, fluorine atoms, methyl groups or trifluoromethyl groups。
Preferably, V is selected, identically or differently, at each occurrence, from any one of the 2-valent organic groups represented by formula 3:
wherein R is 4 -R 15 Are monovalent organic groups, and are each independently selected from any one of hydrogen, fluorine atoms, methyl groups or trifluoromethyl groups; x is a divalent group selected from oxygen atom, methylene group, sulfur atom, sulfone group, carbonyl group, C (CH) 3 ) 2 Or C (CF) 3 ) 2 Any one of the following.
Preferably, U is selected identically or differently from any one of the 4-valent organic groups represented by formula 4 for each occurrence:
wherein R is 16 -R 23 Are monovalent organic groups, and are each independently selected from any one of hydrogen, fluorine atoms, methyl groups or trifluoromethyl groups; y is a divalent group selected from oxygen atom, methylene group, sulfur atom, sulfone group, carbonyl group, C (CH) 3 ) 2 Or C (CF) 3 ) 2 Any one of the following.
Preferably, the component (a) has a structure represented by formula 1-1:
Wherein R is 24 Is selected from CH, identically or differently at each occurrence 2 ＝CH-COOCH 2 CH 2 -or CH 2 ＝C(CH 3 )-COOCH 2 CH 2 -; u, V, W has the same limitations as previously described; j+k is the number of repeating structural units of component (a), and the value of j+k is 3 to 200 (e.g., 3, 5, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120,130. 140, 150, 160, 170, 180, 190 or 200, etc.), preferably 5-100.
Preferably, the component (b) contains at least one compound selected from the group consisting of compounds represented by formula 5-1, formula 5-2, formula 6-1 and/or formula 6-2,
in formula 5-1, R 25 Is alkyl with 1-12 carbon atoms, R 26 Selected from hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, R 27 And R is 28 Each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group;
in formula 5-2, R 29 Selected from hydrogen atoms, -OH, -COOH, -OCH 2 OH、-O(CH 2 ) 2 OH、-COOCH 2 OH or-COO (CH) 2 ) 2 Any one of OH, R 30 And R is 31 Each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, and a tolyl group.
In formula 6-1, R 32 Selected from hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, R 33 And R is 34 Each independently selected from any one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group;
In formula 6-2, R 35 And R is 36 Each independently selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is an integer of 1 to 5 (e.g., 1, 2, 3, 4, or 5), s and t are each independently an integer of 0 to 3 (e.g., 0, 1, 2, or 3), and the sum of s and t is 3.
Preferably, the component (c) is selected from the group consisting of compounds represented by formula 7-1 and/or formula 7-2,
wherein R is 37 Each occurrence of which is identically or differently selected from hydrogen atoms or methyl groups, R 38 Is an alkylene group having 3 to 8 carbon atoms, R 39 And is selected, identically or differently, for each occurrence, from alkylene groups having 1 to 4 carbon atoms (e.g., 1, 2, 3 or 4), n being an integer from 2 to 5, e.g., 2, 3, 4 or 5.
Preferably, the component (d) is selected from the group consisting of compounds represented by formula 8-1 and/or formula 8-2,
in formula 8-1, R 40 Selected identically or differently on each occurrence from hydrogen atoms or monovalent organic groups; r is R 41 Each occurrence of which is identically or differently selected from a hydrogen atom or a monovalent organic group, or R 41 Are combined with each other to form a ring structure;
in formula 8-2, R 42 Selected from hydrogen atoms or monovalent organic radicals, R 43 Selected from monovalent organic groups, d is an integer from 1 to 4 (e.g., 1, 2, 3, or 4), X is selected from single bonds or organic groups of 1 to 4 (e.g., 1, 2, 3, or 4), a is an integer from 1 to 4 (e.g., 1, 2, 3, or 4), b is an integer from 0 to 3 (e.g., 0, 1, 2, or 3), and R is when a is 2, 3, or 4 42 Identical or different, R when b is 2 or 3 43 The same or different.
In the present invention, the alkyl group having 1 to 12 carbon atoms may be an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, and examples of the alkyl group having 1 to 12 carbon atoms may be methyl, ethyl, propyl, isopropyl, butyl, pentyl, octyl, heptyl, decyl, dodecyl or the like.
In the present invention, the cycloalkyl group having 4 to 10 carbon atoms may be a cycloalkyl group having 4, 5, 6, 7, 8, 9 or 10 carbon atoms, and examples of the cycloalkyl group having 4 to 10 carbon atoms may be a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or the like.
Preferably, the content of the component (b) is 0.1 to 10 parts by weight, the content of the component (c) is 1 to 50 parts by weight, and the content of the component (d) is 5 to 30 parts by weight, based on 100 parts by weight of the content of the component (a).
As a preferable embodiment of the present invention, the content of the component (b) may be 0.1 part by weight, 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or the like, the content of the component (c) may be 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, or the like, and the content of the component (d) may be 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, or the like, based on 100 parts by weight of the content of the component (a).
Preferably, the negative photosensitive polyimide composition further contains any one or a combination of at least two of (e) a solvent, (f) an alkoxysilane binder, (g) an anti-rust agent, or (h) a polymerization inhibitor.
Preferably, the content of the (e) solvent is 100 to 200 parts by weight, the content of the (f) alkoxysilane binder is 0.5 to 10 parts by weight, the content of the (g) rust inhibitor is 0.1 to 10 parts by weight, and the content of the (h) polymerization inhibitor is 0.1 to 2 parts by weight, based on 100 parts by weight of the content of the component (a).
As a preferable embodiment of the present invention, the content of the (e) solvent may be 100 parts by weight, 130 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, or the like, the content of the (f) alkoxysilane binder may be 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, or 10 parts by weight, or the like, the content of the (g) rust inhibitor may be 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, or 10 parts by weight, and the content of the (h) polymerization inhibitor may be 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, or 2 parts by weight, or the like, based on 100 parts by weight of the content of the component (a).
In a second aspect, the present invention provides a method for producing a pattern, comprising the steps of applying the negative photosensitive polyimide composition according to the first aspect to a support substrate, and drying, exposing, developing, and heat treating the same.
Preferably, the light source used in the exposure step is i-rays.
In a third aspect, the present invention provides a cured product formed by curing the negative photosensitive polyimide composition according to the first aspect.
In a fourth aspect, the present invention provides an electronic component having the cured product according to the third aspect formed as a surface protective film or an interlayer insulating film.
Compared with the prior art, the invention has the following beneficial effects:
the present invention provides a negative photosensitive polyimide composition developable with an aqueous alkaline solution, in which a portion not exposed to ultraviolet light is easily soluble in the aqueous alkaline solution, and a portion exposed to ultraviolet light is insoluble in the aqueous alkaline solution, thus enabling efficient replication of fine patterns. The negative photosensitive polyimide composition of the present invention has an excellent dissolution rate ratio (contrast) between the unexposed portion and the exposed portion, and has excellent resolution, adhesion, chemical resistance, and storage stability.
Drawings
Fig. 1 is a schematic view of a semiconductor package structure according to the present invention.
Wherein, 1-Si base plate, 2-oxide layer, 3-wafer, 4-first passivation layer, 5-RDL, 6-second passivation layer, 7-Ni, 8-solder bump.
Detailed Description
Hereinafter, embodiments of the negative photosensitive resin composition, the method for producing a cured pattern, the cured product, the interlayer insulating film, the surface protective film, the electronic component, and the like of the present invention will be described in detail. The present invention is not limited to the following embodiments.
[ negative photosensitive resin composition ]
The negative photosensitive polyimide composition of the present invention comprises (a) a solubleA polymer in an aqueous alkaline solution, (b) a photopolymerization initiator, (c) a compound having a polymerizable functional group, and (d) a polymer having a functional group of-CH 2 OR (R is a hydrogen atom OR a monovalent organic group).
The negative photosensitive polyimide composition of the present invention has excellent sensitivity and resolution by increasing the dissolution rate ratio (dissolution contrast) of the exposed portion of the pattern and the unexposed portion with respect to the alkaline developer.
In the case of the polymer soluble in an alkaline aqueous solution as the component (a), the main chain skeleton thereof is preferably a polyimide-based or polyoxazole-based polymer, and particularly preferably an alternating block polymer of two types of polymers, from the viewpoints of processability and heat resistance. The component (a) may be a copolymer having two or more main chain skeletons described above, or a mixture of two or more polymers.
From the viewpoint of the solubility in an aqueous alkaline solution, the polymer soluble in an aqueous alkaline solution of the component (a) is preferably a polymer having a plurality of phenolic hydroxyl groups, a plurality of carboxyl groups, or both groups.
One criterion for the solubility of the component (a) in an aqueous alkaline solution is described below. A coating film having a film thickness of about 5 μm, which is formed by spin-coating a photosensitive composition obtained by dissolving the component (a) alone or together with other components in any solvent on a substrate such as a silicon wafer, was produced. The coating film is immersed in an aqueous solution of tetramethylammonium hydroxide at 20 to 25 ℃. When it is possible to dissolve to form a homogeneous solution, the component (a) used is soluble in an aqueous alkaline solution.
The component (a) is more preferably a polyamide-polyhydroxyamide copolymer, and a polymer having a structural unit represented by the following formula 1, which utilizes alkali solubility of a phenolic hydroxyl group and a part of a carboxyl group, good photosensitivity and film characteristics.
Wherein R is selected from hydrogen, CH, identically or differently for each occurrence 2 ＝CH-COOCH 2 CH 2 -or CH 2 ＝C(CH 3 )-COOCH 2 CH 2 -any one of the following; u is a 4-valent organic group, V is a 2-valent organic group, and W is a 3-valent organic group.
The polyamide containing hydroxyl groups shown in formula 1 can be finally transformed into an oxazol body through curing, dehydrating and ring-closing, and the part containing amide ester can be finally transformed into imide through curing, removing small molecules, so that the cured film has excellent heat resistance, mechanical property and electrical property.
The alkaline aqueous solution refers to an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of metal hydroxide, an aqueous solution of organic amine, or the like.
In formula 1, U is a residue derived from tetracarboxylic dianhydride or a derivative thereof, preferably a 4-valent aromatic group, having an amide ester structure formed by tetracarboxylic dianhydride or a derivative thereof and diamine, preferably tetracarboxylic dianhydride or a derivative thereof having the structure wherein all of 4 bonding sites are present on an aromatic ring, and examples of such tetracarboxylic dianhydride include: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -biphenyl tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride aromatic tetracarboxylic dianhydrides such as 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 9-bis {4- (3, 4-dicarboxyphenoxy) phenyl } fluorene dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, and aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride and 1,2,3, 4-cyclopentane tetracarboxylic dianhydride. These may be used alone or in combination of two or more.
In formula 1, V is a residue derived from a dicarboxylic acid, preferably a 2-valent aromatic group, generally an amide structure of a dicarboxylic acid and a diamine, and preferably a dicarboxylic acid residue having a structure in which 2 binding sites are all present on an aromatic ring, and examples of such dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 4' -dicarboxybiphenyl ether, bis (4-carboxyphenyl) propane, bis (4-carboxyphenyl) hexafluoropropane, and the like. One kind of them may be used alone, or two or more kinds may be combined.
In formula 1, W is a 3-valent organic group, typically a residue derived from a hydroxy diamine, preferably a 3-valent aromatic group, of an amide structure formed by reacting a hydroxy-containing diamine with a dicarboxylic acid, and is preferably a 6-40, more preferably a 6-40, 3-valent aromatic group. The 3-valent aromatic group is preferably a residue of a diamine having the structure in which all of the 3 binding sites are on the aromatic ring and 1 hydroxyl group is located at an ortho position to the bond with W. Examples of such diamines include 2, 4-diaminophenol, 2, 3-diaminophenol, 2, 5-diaminophenol, and 2, 6-diaminophenol. The residue of such diamine is not limited to these, and the residue of these compounds may be two or more kinds alone or in combination.
The solubility of the polymer in an alkaline aqueous solution is derived from a phenolic hydroxyl group and a carboxyl group, and therefore, it is preferable to contain a structure in a proportion of or above. More preferably: j is an amide unit containing a carboxyl group, and the molar ratio of j to k is j=10 to 50 mol%, and k=50 to 90 mol%. The two structural units may be blended or copolymerized. In addition, too large a j cell may result in a loss of film thickness in the exposed area, resulting in an inefficient replication of the pattern. Therefore, by adjusting the amounts of the alkali-soluble groups of the phenolic hydroxyl groups and the carboxyl groups, the dissolution rate of the polymer in the alkali aqueous solution is changed, and thus a negative photosensitive resin composition having a proper dissolution rate can be obtained.
In formula 1-1, R 24 Identical or at each occurrenceIs differently selected from CH 2 ＝CH-COOCH 2 CH 2 -or CH 2 ＝C(CH 3 )-COOCH 2 CH 2 -. j+k is the number of repeating structural units of the polymer of the present invention, preferably 3 to 200, more preferably 5 to 100. When j+k is less than 3, the viscosity of the composition is too small, resulting in the composition not being used as a thick film, and when j+k is more than 200, the composition becomes insoluble in an alkaline aqueous solution. When the structures represented by formula 1 each contain 10% by weight or more of fluorine atoms, water repellency to a proper extent is exhibited at the interface of the film during development with an alkaline aqueous solution, preventing permeation at the interface. However, when the fluorine atom content exceeds 20% by weight, the solubility in an aqueous alkaline solution is reduced. The fluorine atom content is therefore preferably 10 to 20% by weight.
In order to improve adhesion to a substrate, the V moiety may be copolymerized with an aliphatic group having a siloxane structure in a proportion of preferably 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane or bis (p-aminophenyl) octamethylpentasiloxane, as long as heat resistance is not impaired.
The terminal group of the aromatic polyamide represented by formula 1 is carboxylic acid or amine in accordance with the input ratio of U, V to W. One or two kinds of blocking agents may be reacted with the polymer terminals as needed to make one terminal or both terminals each be a saturated aliphatic group, an unsaturated aliphatic group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or the like. In this case, the end capping rate is preferably 30 to 100%.
The molecular weight of the component (a) is preferably 3000 to 200000, more preferably 5000 to 100000 in terms of weight average molecular weight. The molecular weight herein is a value measured by gel permeation chromatography and converted from a standard polystyrene standard curve.
In the present invention, the polyamide having the structural unit represented by formula 1 is generally obtained by first acylating a dicarboxylic acid and a diamine having a hydroxyl group to synthesize an amino-terminated compound, then subjecting the compound to polycondensation with an acid anhydride to form a polyamic acid structure, and thereafter carrying out imidization and then esterification.
Specifically, in the first step, the diamine compound having a hydroxyl group can be produced by reacting a dicarboxylic acid with a diamine having a hydroxyl group. And secondly, carrying out polycondensation reaction on the diamine compound synthesized in the first step and anhydride to prepare polyamide acid. In the third step, the polyamic acid is converted to a polyisoimide in the presence of a dehydrating agent, preferably trifluoroacetic anhydride. And fourthly, combining the characteristic of acid anhydride of the isoamide, and adding hydroxyethyl acrylate or hydroxyethyl methacrylate to perform esterification reaction to prepare the polymer shown in the formula 1.
The compound which generates a radical upon irradiation with active light as the component (b) is a photoinitiator. The active light rays include ultraviolet rays such as i-rays, visible rays, and radiation. The component (b) may be: oxime compounds, acylphosphorus oxide compounds, acyldialkyl methane compounds, and the like. Preferably, the composition contains one or more compounds selected from the group consisting of the compounds represented by formula 5-1 and/or formula 5-2 (hereinafter referred to as component (b 1)). The component (b 1) is preferably a component having high sensitivity to active light, and is preferably a sensitizer having high sensitivity.
In formula 5-1, R 25 Is alkyl with 1-12 carbon atoms, R 26 Selected from hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, R 27 And R is 28 Each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group;
in formula 5-2, R 29 Selected from hydrogen atoms, -OH, -COOH, -OCH 2 OH、-O(CH 2 ) 2 OH、-COOCH 2 OH or-COO (CH) 2 ) 2 Any one of OH, R 30 And R is 31 Each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, and a tolyl group.
As the compound represented by the formula 5-1, a compound represented by the following formula 5-1-1, which is commercially available under the name "IRGACURE OXE 02" manufactured by BASF, is exemplified.
The compound represented by the formula 5-2 is a compound represented by the following formula 5-2-1, which is commercially available under the name "IRGACURE OXE 01" manufactured by BASF, and the compound represented by the following formula 5-2-2, which is commercially available under the name "NCI-930" manufactured by ADEKA.
The component (b) preferably contains one or more compounds selected from the compounds represented by the following formulas 6-1 and/or 6-2 (hereinafter referred to as component (b 2)). Component (b 2) is preferably a component having low sensitivity to active light, and is preferably a sensitizer having standard sensitivity.
In formula 6-1, R 32 Selected from hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, R 33 And R is 34 Each independently selected from any one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group;
in formula 6-2, R 35 And R is 36 Each independently selected from hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, m is an integer of 1 to 5 (e.g., 1, 2, 3, 4, or 5), s and t are each independently an integer of 0 to 3, and the sum of s and t is 3.
As the compound represented by the formula 6-1, a compound represented by the following formula 6-1-1, which is commercially available under the name "G-1820 (PDO)" manufactured by Lambson, is exemplified.
As the compound represented by the formula 6-2, there is mentioned a compound represented by the following formula 6-2-1, which is commercially available under the trade name "IRGCURE TPO" manufactured by BASF. In addition, a compound represented by the following formula 6-2-2, which is commercially available under the trade name "IRGCURE819" manufactured by BASF, may be mentioned.
The component (b) may be used alone or in combination of two or more. Preferably, the composition contains at least one selected from the group consisting of the component (b 1) and the component (b 2). More preferably, component (b 1) and component (b 2) are contained. The content of the component (b 1) is usually 0.05 to 5 parts by mass, preferably 0.05 to 1 part by mass, more preferably 0.15 to 0.6 part by mass, relative to 100 parts by mass of the component (a); the content of the component (b 2) is usually 0.5 to 10 parts by mass, preferably 0.5 to 5 parts by mass.
When the components (b 1) and (b 2) are contained, the total amount of the two components is preferably 0.6 to 11 parts by mass, more preferably 1 to 6 parts by mass, and still more preferably 1.15 to 5.6 parts by mass.
The component (c) is selected from the compounds represented by the formula 7-1 and/or the formula 7-2,
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wherein R is 37 Each occurrence of which is identically or differently selected from hydrogen atoms or methyl groups, R 38 Is an alkylene group having 3 to 8 carbon atoms, R 39 And is selected, identically or differently, for each occurrence, from alkylene groups having 1 to 4 carbon atoms, n being an integer from 2 to 5.
Specific examples of the component (c) include: diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, and the like. One kind may be used alone, or two or more kinds may be combined.
The blending amount of the component (c) is preferably 5 to 50 parts by mass, more preferably 10 to 35 parts by mass, relative to 100 parts by mass of the component (a). Within the above range, good adhesion can be exhibited.
As component (d), it has-CH 2 A crosslinking agent having an OR (R is a hydrogen atom OR a 1-valent organic group) group, which is crosslinked by reacting with the polymer as the component (a) in the heat treatment step after the photosensitive polymer composition of the present invention is applied, exposed and developed, OR which is a compound which is self-polymerized in the heat treatment step. In addition, the crosslinking agent as the component (d) has affinity for the alkaline aqueous solution, and can increase the dissolution rate of the alkaline aqueous solution.
In the present invention, component (d) is a compound having a structure of-CH 2 OR (R is a hydrogen atom OR a 1-valent organic group). The number of the groups in the compound may be one or more, but is preferably two or more. Wherein component (d) is selected from the compounds represented by the following formula 8-1 and/or formula 8-2,
in formula 8-1, R 40 Selected identically or differently on each occurrence from hydrogen atoms or monovalent organic groups; r is R 41 Each occurrence of which is identically or differently selected from a hydrogen atom or a monovalent organic group, or R 41 Are combined with each other to form a ring structure;
in formula 8-2, R 42 Selected from hydrogen atoms or monovalent organic radicals, R 43 Selected from monovalent organic groups, d is an integer from 1 to 4, X is selected from a single bond or an organic group of 1 to 4 valency, a is an integer from 1 to 4 B is an integer of 0 to 3, R when a is 2, 3 or 4 42 Identical or different, R when b is 2 or 3 43 The same or different.
Specific examples of the compound represented by formula 8-1 are shown below. In addition, two or more of these compounds may be used singly or in combination.
In the formula 8-1-1, R 48 Each occurrence of which is identically or differently selected from alkyl groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, R 49 And is selected, identically or differently, for each occurrence, from alkyl groups having from 1 to 10 carbon atoms.
Examples of the 1-4 valent organic group of X in the formula 8-2 include an alkyl group having 1 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms (e.g., ethylene group, etc.), an arylene group having 6 to 30 carbon atoms (e.g., phenylene group, etc.), or a group obtained by substituting some or all of these hydroxyl hydrogen atoms with halogen atoms such as fluorine atoms, and these groups may further contain phenyl groups, sulfone groups, carbonyl groups, ether linkages, thioether linkages, amide linkages, etc. R is R 42 Preferably hydrogen, alkyl or alkenyl. The number of carbon atoms of the alkyl group or alkenyl group is preferably 1 to 20.R is R 43 Preferably alkyl, alkenyl, alkoxyalkyl or hydroxymethyl, and the number of carbon atoms is preferably 1 to 20.
The purity of the compound represented by the above formula 8-2 is preferably 75% or more, more preferably 85% or more. When the purity is 85% or more, the storage stability is excellent, and the crosslinking reaction of the resin composition can be sufficiently performed. Further, since unreacted groups that become water-absorbent groups can be reduced, the water absorbency of the resin composition can be reduced. Examples of the method for obtaining the high-purity thermal crosslinking agent include recrystallization and distillation. The purity of the thermal crosslinking agent can be determined by liquid chromatography.
Specific examples of the compound represented by formula 8-2 are shown below. In addition, two or more of these compounds may be used singly or in combination.
The content of the thermal crosslinking agent in the component (d) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the resin in the component (a). When the amount is 5 parts by weight or more, the crosslinking density of the cured film is increased, and when it is 10 parts by weight or more, the chemical resistance is higher, and at the same time, higher mechanical properties can be obtained. In addition, from the viewpoint of the storage stability and mechanical strength of the composition, it is preferably 30 parts by mass or less.
The resin composition of the present invention further contains (e) a solvent, preferably an organic solvent. Examples include: polar solvents such as gamma-butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylsulfoxide, hexamethylphosphoric triamide, dimethylimidazolidinone, tetraethylurea, tetramethylurea, ethyl lactate, 3-methoxy-N, N-dimethylpropaneamide, and N-acetyl-epsilon-caprolactam.
As the component (e), for example, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can be used. Specifically, for example, it is possible to use: acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methylene chloride, 1, 2-dichloroethane, 1, 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, propylene glycol 1-monomethyl ether 2-acetate, and the like. The component (e) may be used alone or in combination of two or more. When component (e) is contained, the blending amount of component (e) is preferably 50 to 1000 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of component (a).
The resin composition of the present invention further contains (f) an adhesion promoter, typically an organosilane compound, and examples of the organosilane compound include: gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, vinyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-acryloxypropyl trimethoxysilane, gamma-ureidopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, bis (2-hydroxyethyl) -3-aminopropyl triethoxysilane, triethoxysilylpropyl ethyl carbamate, 3- (triethoxysilyl) propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3-triethoxysilyl-N- (l, 3-dimethylbutylidene) propylamine, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, and the like.
When the organosilane compound is contained, adhesion between the photosensitive resin composition and the substrate after curing can be improved. When the organosilane compound is contained, the content of the organosilane compound is more preferably 0.5 to 15 parts by mass, still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the component (a).
The photosensitive resin composition of the present invention may contain a rust inhibitor from the viewpoint of further improving the rust inhibitive performance. Examples of the rust inhibitor include: 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole, and the like. These tetrazolium compounds may also be water-soluble salts thereof.
The content of the rust inhibitor is preferably 1 to 10 parts by mass, more preferably 0.5 to 4.0 parts by mass, based on 100 parts by mass of the component (a).
The photosensitive resin composition of the present invention may contain a polymerization inhibitor. As the polymerization inhibitor, known compounds such as 1, 4-trimethyl-2, 3-diazabicyclo [3.2.2] -non-2-ene-N, N-dioxide and the like can be used. The content of the polymerization inhibitor is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 2.0 parts by mass, based on 100 parts by mass of the component (a).
The present invention may further contain a surfactant, thereby improving coatability with the substrate. Examples of the surfactant include fluorine-based surfactants such as fluoroad (trade name, manufactured by Sumitomo 3M (Co., ltd.), megafac (trade name, manufactured by DIC (Co., ltd.), surflon (trade name, manufactured by Asahi Kabushiki Kaisha); organosiloxane surfactants such as KP341 (trade name, manufactured by Xinyue chemical industry Co., ltd.), DBE (trade name, manufactured by Chisso Corporation), polyflow, glanol (trade name, manufactured by Kagaku chemical Co., ltd.), BYK (trade name, manufactured by BYK-Chemie GmbH); and acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyowa Kagaku Co., ltd.).
Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, the photosensitive resin composition can be obtained by uniformly mixing the above-mentioned components (a) to (d), and if necessary, components (e) to (h), a surfactant, and the like. The dissolution method includes stirring and heating. In the heating, the heating temperature is preferably set within a range that does not deteriorate the performance of the resin composition, and is usually room temperature to 80 ℃. The dissolution order of the components is not particularly limited, and includes, for example, a method of sequentially dissolving compounds having low solubility. In addition, as for the components such as the surfactant and a part of the adhesion improver which are liable to generate bubbles when dissolved by stirring, it is possible to prevent dissolution failure of other components due to generation of bubbles by adding them last after dissolving other components.
The obtained photosensitive resin composition is preferably filtered using a filter to remove impurities and particles. The filter pore size is 0.5 to 0.02. Mu.m, for example, but not limited to, 0.5. Mu.m, 0.2. Mu.m, 0.1. Mu.m, 0.05. Mu.m, 0.02. Mu.m, etc. The filter material includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., preferably polyethylene or nylon. When inorganic particles are contained in the photosensitive resin composition, a filter having a larger pore diameter than the particle diameter of the inorganic particles is preferably used.
[ cured product ]
The cured product of the present invention can be obtained by curing the negative photosensitive polyimide composition. The cured product of the present invention can be used as a patterned cured film or an unpatterned cured film.
The method for producing a pattern cured film includes: a step (film forming step) of forming a photosensitive resin film by applying the negative photosensitive polyimide composition on a substrate and drying the composition; a step of exposing the photosensitive resin film (exposure step); a step (developing step) of developing the exposed photosensitive resin film with an aqueous alkali solution to form a patterned resin film; and a step of heating the pattern resin film (heating step). The method for producing the unpatterned cured film includes, for example, the film forming step and the heating step. The method may further comprise an exposure step.
In the film forming step, the negative photosensitive polyimide composition is applied to a metal substrate such as Cu, a glass substrate, a semiconductor, or a metal oxide insulator (e.g., tiO) by, for example, dipping, spraying, screen printing, spin coating, or the like 2 、SiO 2 Etc.), silicon nitride, etc. From the viewpoint of handleability, the applied negative photosensitive polyimide composition may be dried by heating (for example, 90 to 150 ℃ for 1 to 5 minutes) using a hot plate, an oven, or the like. The support substrate may be cleaned with acetic acid or the like before coating. The film thickness of the photosensitive resin film is preferably 5 to 20. Mu.m.
In the exposure step, for example, the photosensitive resin film formed on the substrate is irradiated with the active light rays through a mask. From the viewpoint of transparency of the component (a), irradiation with i-rays can be suitably used. After exposure, post-exposure heating (PEB) may be performed as needed. The post-exposure heating temperature is preferably 70 to 140℃and the post-exposure heating time is preferably 1 to 5 minutes.
In the developing step, for example, the exposed portion of the photosensitive resin film after the exposing step is removed with a developing solution, thereby patterning the photosensitive resin film. In the case of the alkali-soluble photosensitive resin composition, for example, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) or the like can be suitably used as the developer. The alkali concentration of these aqueous solutions is preferably set to 0.1 to 10 mass%. Further, alcohols or surfactants may be added to the developer. These may be blended in a range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the developer. The patterned photosensitive resin film is referred to as a pattern resin film.
In the heating step, the pattern resin film or the photosensitive resin film is heated to cure the photosensitive resin composition. Particularly, a film obtained by curing a pattern resin film is called a pattern cured film. The heating temperature is preferably 100 to 500 ℃, and from the viewpoint of sufficiently preventing damage to the electronic component caused by heat, it is preferably 250 ℃ or less, more preferably 225 ℃ or less, and still more preferably 140 to 210 ℃. The heating time is preferably 20 minutes to 6 hours, more preferably 30 minutes to 3 hours. Multi-stage heating may also be performed. The heat treatment may be performed using, for example, an oven such as a quartz tube oven, a hot plate, a rapid annealing furnace (rapid thermal anneal), a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, or a microwave curing furnace. In addition, although either the atmosphere or an inert atmosphere such as nitrogen may be selected, the inert atmosphere such as nitrogen is preferable because oxidation of the pattern can be prevented when the pattern is performed under nitrogen.
The cured product of the present invention can be used as an interlayer insulating film, a surface protective film, or the like.
The interlayer insulating film and the surface protective film of the present invention can be used for electronic components and the like, and the electronic components of the present invention can be used for semiconductor devices and the like. The semiconductor device can be used for various electronic equipment and the like, and a schematic view of the semiconductor package structure of the present invention is shown in fig. 1.
This gives excellent rust preventing effect and adhesion effect to the support substrate (particularly copper substrate and copper alloy substrate), and can suppress discoloration of the cured film and the support substrate (particularly copper substrate and copper alloy substrate).
Examples of the semiconductor device include a semiconductor package such as a Wafer Level Chip Size Package (WLCSP) and a fan-out wafer level package (FOWLP). The interlayer insulating film and the surface protective film of the present invention can be used for a circuit-forming substrate which can be used for a suspension for a hard disk drive, a flexible wiring board, or the like.
Examples (example)
The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The resins and photosensitive resin compositions in examples and comparative examples were evaluated by the following methods.
The shorthand names of the compounds, auxiliaries and solvents shown in the following examples and comparative examples are as follows.
IPDC: isophthaloyl dichloride
4-NAP: 2-amino-4-nitrophenols
SiDA:1, 3-bis (3-aminopropyl) tetramethyldisiloxane
ODPA:4,4' -Oxyphthalic anhydride
DMAP:4,4 '-diamino-2, 2' -dimethylbiphenyl
TFAA: trifluoroacetic anhydride
HEMA: hydroxyethyl methacrylate
MAP: m-aminophenol
NMP: n-methyl-2-pyrrolidone
GBL; gamma-butyrolactone
TMAH: tetramethyl ammonium hydroxide
DCC: dicyclohexylcarbodiimide
Synthesis example 1: preparation of diamines containing hydroxyl groups
30.8g (0.2 mol) of 4-NAP was dissolved in 200mL of acetone under a stream of dry nitrogen, and the resulting solution was then cooled to-10 ℃. Subsequently, 200mL of an acetone solution of 22.4g (0.11 mol) of IPDC was added dropwise thereto so that the temperature of the reaction solution did not exceed 0 ℃. After the addition was completed, the reaction mixture was returned to room temperature, and the precipitated white solid was filtered off and dried under vacuum at 50 ℃.
30g of solid was put into a 1000mL three-necked flask, dispersed in 800mL of a methyl-fiber-melting agent, 3g of 5% palladium on carbon was added thereto, and the temperature was raised to 60 ℃. 7g of hydrazine hydrate was slowly dropped into the mixture, and the mixture was stirred at 60℃for 1 hour. After completion of stirring, the catalyst was removed by filtration, concentrated to 200mL under reduced pressure, and the precipitate was collected by pouring into 1.5L of water, followed by vacuum drying at 50℃for 20 hours to obtain diamine compound (I), and the obtained solid was directly used for the reaction.
Synthesis example 2: synthesis of Polymer A
8.31g (0.022 mol) of the diamine (I) obtained in Synthesis example 1, 1.24g (0.005 mol) of SiDA were dissolved in 50g of NMP under a stream of dry nitrogen, 9.31g (0.030 mol) of ODPA and 14g of NMP were added together, and the reaction was continued at 20℃for 1 hour, and then continued at 40℃for 2 hours. After that, 0.65g (0.006 mol) of MAP as a capping agent was added, and then the reaction was continued at 40℃for 1 hour. Thereafter 6.84g (0.06 mol) of TFAA are added and the reaction is continued at 40℃for 4 hours. Thereafter, 7.81g (0.06 mol) of HEMA was added dropwise thereto, and the reaction was continued at 40℃for 4 hours. After the reaction was completed, the solution was poured into 2L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80℃for 72 hours to give polymer A. The polymer A was subjected to molecular weight measurement and esterification rate measurement, and the test method was as follows:
(1) Determination of molecular weight
The number average molecular weight was determined under the following conditions by Gel Permeation Chromatography (GPC) based on standard polystyrene conversion. The number average molecular weight of polymer A was 42,000. The measurement was performed using 1mL of a solution with respect to 0.5mg a of the solvent [ Tetrahydrofuran (THF)/Dimethylformamide (DMF) =1/1 (volume ratio) ].
Measurement device: l4000UV manufactured by Hitachi of Detector Co., ltd
And (3) a pump: l6000 manufactured by Hitachi Co., ltd
C-R4A Chromatopac manufactured by Shimadzu corporation
Measurement conditions: chromatographic column Gelpack GL-S300 MDT-5X 2
Eluent: THF/DMF=1/1 (volume ratio), liBr (0.03 mol/L), H3PO4 (0.06 mol/L)
Flow rate: 1.0mL/min, detector: UV270nm
(2) Determination of esterification Rate
Further, the esterification ratio of a (the reaction esterification ratio of carboxyl groups of ODPA and HEMA was 80 mol% with respect to all carboxyl groups of polyamic acid (the remaining 20 mol% is carboxyl groups) was calculated by NMR measurement under the following conditions.
Measurement device: AV400M manufactured by Bruker Biospin Co
Magnetic field strength: 400MHz
Reference substance: tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)
Synthesis example 3: synthesis of Polymer B
8.31g (0.022 mol) of the diamine (I) obtained in Synthesis example 1, 1.24g (0.005 mol) of SiDA were dissolved in 50g of NMP under a stream of dry nitrogen, 9.31g (0.030 mol) of ODPA and 14g of NMP were added together, and the reaction was continued at 20℃for 1 hour, and then continued at 40℃for 2 hours. After that, 0.65g (0.006 mol) of MAP as a capping agent was added, and then the reaction was continued at 40℃for 1 hour. After the reaction was completed, the solution was poured into 2L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80℃for 72 hours to give polymer B. The number average molecular weight was 38000 and the esterification rate was 0% as measured by the method of Synthesis example 2.
Synthesis example 4: synthesis of Polymer C
Under a stream of dry nitrogen, 4.67g (0.022 mol) of DMAP and 1.24g (0.005 mol) of SiDA were dissolved in 50g of NMP, 21.4g (0.030 mol) of ODPA and 14g of NMP were added together, and the reaction was continued at 20℃for 1 hour, and then continued at 40℃for 2 hours. After that, 0.65g (0.006 mol) of MAP as a capping agent was added, and then the reaction was continued at 40℃for 1 hour. Thereafter 6.84g (0.06 mol) of TFAA are added and the reaction is continued at 40℃for 4 hours. Thereafter, 7.81g (0.06 mol) of HEMA was added dropwise thereto, and the reaction was continued at 40℃for 4 hours. After the reaction was completed, the solution was poured into 2L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80℃for 72 hours to give polymer C. The number average molecular weight was 38000 and the esterification rate was 80% as measured by the method of Synthesis example 2.
Examples 1 to 10 and comparative examples 1 to 2
Photosensitive resin compositions of examples 1 to 10 and comparative examples 1 to 2 were prepared according to the components and blending amounts shown in tables 1 and 2. The amounts of the components in tables 1 and 2 are based on 100 parts by mass of the component (a).
The components used are as follows.
Component (b): photoinitiator
b1: IRUGCURE OXE 02 (manufactured by BASF, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (0-acetyl oxime))
b2: g-1820 (PDO) (1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, manufactured by Campson Co., ltd.)
Component (c): polymerizable monomers
c1: tetraethylene glycol dimethacrylate
c2: pentaerythritol tetraacrylate
Component (d): thermal crosslinking agent
Component (e): solvent(s)
e1: GBL (gamma-butyrolactone)
e2: NMP (N-methyl-2-pyrrolidone)
Component (f): silane coupling agent
f1: gamma-ureidopropyltriethoxysilane
f2: vinyl triethoxysilane
Component (g): rust inhibitor
g1: 5-amino tetranitrogen file
Component (h): polymerization inhibitor
h1: nitrosodiphenylamine
TABLE 1
TABLE 2
The photosensitive resin compositions produced in examples and comparative examples were evaluated for performance by the following methods:
(1) Production of developing film
The photosensitive resin compositions (varnishes) produced in examples and comparative examples were spin-coated on 8-inch silicon wafers, and then heat-treated (prebaked) at 120℃for 2 minutes using a hot plate (manufactured by Tokyo Electron Ltd., coating and developing apparatus Mark-7) to produce prebaked films having a thickness of 2.5. Mu.m. Using an i-line stepper (manufactured by Nikon Corporation, NSR-2005i 9C) at a rate of 50 to 400mJ/cm 2 Exposure of 10mJ/cm 2 The resulting pre-baked film is exposed to light. After exposure, the negative photosensitive resin composition was exposed to light at 100℃for 1 minute and then baked. After the negative photosensitive resin composition was subjected to post-exposure baking, it was developed with a 2.38 wt% aqueous solution of Tetramethylammonium (TMAH) (manufactured by mitsubishi gas chemistry, ELM-D) for 60 seconds, and then rinsed with pure water to obtain a developed film.
(2) Method for measuring film thickness
The film thicknesses after pre-baking and development were measured at refractive indices of 1.63 using a light interference film thickness measuring device LAMBDA ACE STM-602 manufactured by Dainippon Screen mfg.Co., ltd.
(3) Calculation of developing film loss amount
The amount of loss of the developing film was calculated according to the following formula. Since the film thickness after prebaking is 2.5 μm, the developing film loss amount is preferably less than 0.50 μm. The case where the loss amount of the developing film was less than 0.50 μm was judged as "A", the case where 0.51 to 0.59 μm was judged as "B", and the case where 0.60 μm or more was judged as "C".
Development film loss amount (μm) =film thickness after prebaking-film thickness after development. The results are shown in Table 3.
(4) Evaluation of residual film Rate after curing
In the production of the cured product, the film thickness after heating on a heating plate at 110℃for 4 minutes and the film thickness after curing (the same applies to the measurement of the film thickness) were measured using Filmetrics (manufactured by Filmetrics). The film thickness after curing was 10 μm divided by the film thickness after heating on a heating plate at 110℃for 4 minutes, and then converted into a percentage, whereby the residual film rate after curing was determined. The results are shown in Table 3.
(5) Sensitivity evaluation
After exposure and development, an exposure amount (referred to as an optimal exposure amount Eop) of a line and space pattern (1L/1S) of 20 μm was formed with a width of 1 to 1 as sensitivity. If the Eth is 200mJ/cm 2 Hereinafter, it can be determined as high sensitivity. More preferably 150mJ/cm 2 The following is given. The results are shown in Table 3.
(6) Evaluation of chemical resistance
GTN-68P (manufactured by Qianzhi Metal industries Co., ltd.) was applied to the above-mentioned cured product by a pipette. The coated cured product was placed on a hot plate at 245 ℃ and held for 1 minute. Thereafter, the solidified material was transferred from the heating plate and cooled to room temperature. The cooled solidified product was washed with isopropyl alcohol and dried, and then the film thickness was measured.
The film thickness change rate (%) was calculated from the film thickness change before and after GTN-68P coating. If the value is positive, this means that the membrane swells, and if the value is negative, this means that the membrane dissolves. The results are shown in Table 3.
(7) Evaluation of adhesion
With the above method for producing a cured product, a cured product was produced on a Cu substrate, and the obtained cured product was cut into 10×10 checkered cuts by a shearing blade using a cross cut guide (manufactured by COAT-TECH corporation), thereby dividing the cured product into 100 pieces.
An adhesive tape (manufactured by 3M japan corporation) was attached to the cured product, and the adhesive tape was peeled off. The adhesiveness was evaluated as follows based on the number of chips of the cured product peeled from the substrate when the adhesive tape was peeled off.
A: the residual lattice is 100 to 80.
B: the remaining lattice is less than 80.
The results are shown in Table 3.
TABLE 3 Table 3
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As can be seen from Table 3, the photosensitive resin compositions provided in examples 1 to 10 of the present invention all had a small loss of developing film, a low residual film rate (55% -78%) after curing, and excellent chemical resistance and adhesion. Compared with the examples, the developing film of comparative example 1 has a higher loss amount, a higher residual film rate after curing, and poor chemical resistance. Whereas comparative example 2 could not be developed.
Industrial applicability
The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a covercoat, a surface protective film, or the like, and the interlayer insulating film, the covercoat, or the surface protective film of the present invention can be used for electronic components, or the like.
While the foregoing detailed description has described several embodiments and/or examples of the invention, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments and/or examples without materially departing from the novel teachings and effects of this invention. Accordingly, these variations are also included in the scope of the present invention.

Claims (10)

1. A negative photosensitive polyimide composition, characterized in that the negative photosensitive polyimide composition contains the following components (a), (b), (c) and (d):
(a) A polymer soluble in an aqueous alkaline solution;
(b) A photopolymerization initiator;
(c) A compound having a polymerizable functional group including an unsaturated double bond or a triple bond;
(d) A thermal crosslinking agent.
2. The negative photosensitive polyimide composition according to claim 1, wherein the component (a) has a structural unit represented by formula 1,
wherein R is selected from hydrogen, CH, identically or differently for each occurrence 2 ＝CH-COOCH 2 CH 2 -or CH 2 ＝C(CH 3 )-COOCH 2 CH 2 -any one of the following; u is a 4-valent organic group, V is a 2-valent organic group, and W is a 3-valent organic group.
3. The negative photosensitive polyimide composition according to claim 2, wherein W is selected from any one of 3-valent organic groups represented by formula 2, identically or differently, for each occurrence:
wherein R is 1 -R 3 Are monovalent organic groups, and are each independently selected from any one of hydrogen, fluorine atoms, methyl groups or trifluoromethyl groups;
preferably, V is selected, identically or differently, at each occurrence, from any one of the 2-valent organic groups represented by formula 3:
wherein R is 4 -R 15 Are monovalent organic groups, and are each independently selected from any one of hydrogen, fluorine atoms, methyl groups or trifluoromethyl groups; x is a divalent group selected from oxygen atom, methylene group, sulfur atom, sulfone group, carbonyl group, C (CH) 3 ) 2 Or C (CF) 3 ) 2 Any one of them;
preferably, U is selected identically or differently from any one of the 4-valent organic groups represented by formula 4 for each occurrence:
wherein R is 16 -R 23 Are monovalent organic groups, and are each independently selected from any one of hydrogen, fluorine atoms, methyl groups or trifluoromethyl groups; y is a divalent group selected from oxygen atom, methylene group, sulfur atom, sulfone group, carbonyl group, C (CH) 3 ) 2 Or C (CF) 3 ) 2 Any one of them;
preferably, the component (a) has a structure represented by formula 1-1:
wherein R is 24 Is selected from CH, identically or differently at each occurrence 2 ＝CH-COOCH 2 CH 2 -or CH 2 ＝C(CH 3 )-COOCH 2 CH 2 -; u, V, W has the same limitations as claim 2; j+k is the number of repeating structural units of component (a), and the value of j+k is 3 to 200, preferably 5 to 100.
4. The negative photosensitive polyimide composition according to any of claims 1 to 3, wherein the component (b) contains one or more compounds selected from the group consisting of compounds represented by formula 5-1, formula 5-2, formula 6-1 and/or formula 6-2,
in formula 5-1, R 25 Is alkyl with 1-12 carbon atoms, R 26 Selected from hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, R 27 And R is 28 Each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group;
In formula 5-2, R 29 Selected from hydrogen atoms, -OH, -COOH, -OCH 2 OH、-O(CH 2 ) 2 OH、-COOCH 2 OH or-COO (CH) 2 ) 2 Any one of OH, R 30 And R is 31 Each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group;
in formula 6-1, R 32 Selected from hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, R 33 And R is 34 Each independently selected from any one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group;
in formula 6-2, R 35 And R is 36 Each independently selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is an integer of 1 to 5, s and t are each independently an integer of 0 to 3, and the sum of s and t is 3.
5. The negative photosensitive polyimide composition according to any one of claims 1 to 4, wherein the component (c) is selected from the group consisting of compounds represented by formula 7-1 and/or formula 7-2,
wherein R is 37 Each occurrence of which is identically or differently selected from hydrogen atoms or methyl groups, R 38 Is an alkylene group having 3 to 8 carbon atoms, R 39 And is selected, identically or differently, for each occurrence, from alkylene groups having 1 to 4 carbon atoms, n being an integer from 2 to 5.
6. The negative photosensitive polyimide composition according to any one of claims 1 to 5, wherein the component (d) is selected from the group consisting of compounds represented by formula 8-1 and/or formula 8-2,
In formula 8-1, R 40 Selected identically or differently on each occurrence from hydrogen atoms or monovalent organic groups; r is R 41 Each occurrence of which is identically or differently selected from a hydrogen atom or a monovalent organic group, or R 41 Are combined with each other to form a ring structure;
in formula 8-2, R 42 Selected from hydrogen atoms or monovalent organic radicals, R 43 Selected from monovalent organic groups, d is an integer from 1 to 4, X is selected from a single bond or an organic group of 1 to 4 valency, a is an integer from 1 to 4, b is an integer from 0 to 3, when a is 2, 3 or 4, R 42 Identical or different, R when b is 2 or 3 43 The same or different.
7. The negative photosensitive polyimide composition according to any one of claims 1 to 6, wherein the content of the component (b) is 0.1 to 10 parts by weight, the content of the component (c) is 1 to 50 parts by weight, and the content of the component (d) is 5 to 30 parts by weight, based on 100 parts by weight of the content of the component (a);
preferably, the negative photosensitive polyimide composition further contains any one or a combination of at least two of a solvent, an alkoxysilane binder, an antirust agent, or a polymerization inhibitor;
preferably, the content of the solvent is 100 to 200 parts by weight, the content of the alkoxysilane binder is 0.5 to 10 parts by weight, the content of the rust inhibitor is 0.1 to 10 parts by weight, and the content of the polymerization inhibitor is 0.1 to 2 parts by weight, based on 100 parts by weight of the content of the component (a).
8. A method for producing a pattern, comprising the steps of applying the negative photosensitive polyimide composition according to any one of claims 1 to 7 to a supporting substrate, and drying, exposing, developing, and heat-treating the composition;
preferably, the light source used in the exposure step is i-rays.
9. A cured product formed by curing the negative photosensitive polyimide composition according to any one of claims 1 to 7.
10. An electronic component comprising the cured product according to claim 9, which is formed as a surface protective film or an interlayer insulating film.
CN202210491940.XA 2022-05-07 2022-05-07 Negative photosensitive polyimide composition, method for producing pattern, and electronic component Pending CN117055288A (en)

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