CN111819493A - Photosensitive resin composition, dry film, cured product, printed wiring board, and semiconductor element - Google Patents
Photosensitive resin composition, dry film, cured product, printed wiring board, and semiconductor element Download PDFInfo
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- CN111819493A CN111819493A CN201980016724.6A CN201980016724A CN111819493A CN 111819493 A CN111819493 A CN 111819493A CN 201980016724 A CN201980016724 A CN 201980016724A CN 111819493 A CN111819493 A CN 111819493A
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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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
- G03F7/20—Exposure; Apparatus therefor
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Provided are a photosensitive resin composition which can be cured at a low temperature of less than 300 ℃ and can give a cured product having improved chemical resistance and elongation, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, a semiconductor element, a printed wiring board, and an electronic component having the cured product. Provided is a photosensitive resin composition or the like, characterized by comprising: (A) alkali soluble resinA photosensitizer (B), and a polyether compound (C) containing 100 to 10,000 polymerization units represented by the general formula (1). (in the general formula (1), X represents C1-10 alkylene.)
Description
Technical Field
The present invention relates to a photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a semiconductor element, which are suitable for a protective film of a semiconductor device, an insulating film for a redistribution layer of a Wafer Level Package (WLP), an insulating portion of a passive component, and the like.
Background
A cured film of a photosensitive resin composition containing a precursor of a heat-resistant resin such as polyimide or Polybenzoxazole (PBO) is used for a buffer coating film of LSI and an insulating film for a rewiring layer of a Wafer Level Package (WLP). These photosensitive resin compositions are cured by heat treatment for cyclizing a precursor of a heat-resistant resin. The conventional heat treatment is 300 ℃ or higher, but in recent years, in order to suppress thermal damage to the semiconductor element, it has been desired to cure a precursor of a heat-resistant resin at a low temperature.
In this regard, previously discussed: in order to obtain a photosensitive resin composition curable at low temperature, a crosslinking agent containing a methylol group in its structure is contained, and the crosslinking agent and the resin are crosslinked at low temperature, thereby improving the properties of a cured film. For example, as a positive photosensitive resin composition curable at low temperature, there is a resin composition containing a melamine-based or urea-based crosslinking agent (patent document 1).
On the other hand, for a cured product of the photosensitive resin composition as described above, elongation (elongation at break) is also required in order to ensure mechanical and thermal shock reliability.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4046563
Disclosure of Invention
Problems to be solved by the invention
When a melamine-based or urea-based crosslinking agent is compounded, low-temperature curing can be achieved, but in order to have sufficient chemical resistance, a large amount of the crosslinking agent must be added, and as a result, the crosslinking density increases, and the elongation decreases.
Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of obtaining a cured product which is cured at a low temperature of less than 300 ℃ and has improved chemical resistance and elongation, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, a semiconductor element, a printed circuit board, and an electronic component having the cured product.
Means for solving the problems
The present inventors have conducted extensive studies and, as a result, have found that the above problems can be solved by including a specific polyether compound in a photosensitive resin composition, and have completed the present invention.
That is, the photosensitive resin composition of the present invention is characterized by comprising: (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a polyether compound containing 100 to 10,000 polymerized units represented by the general formula (1).
(in the general formula (1), X represents C1-10 alkylene.)
The photosensitive resin composition of the present invention preferably further contains 1 to 1,000 polymerized units represented by the general formula (2) in the polyether compound (C).
(in the general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms, wherein the same condition as that of X in the general formula (1) is not included.)
The photosensitive resin composition of the present invention preferably further contains 1 to 1,000 polymerized units represented by the general formula (3) in the polyether compound (C).
(in the general formula (3), Z represents C1-10 alkylene having a reactive functional group or phenyl in a side chain.)
The photosensitive resin composition of the present invention preferably contains a polybenzoxazole precursor as the aforementioned alkali-soluble resin (a).
The photosensitive resin composition of the present invention preferably contains a naphthoquinone diazide compound as the aforementioned (B) photosensitizer.
The dry film of the present invention is characterized by comprising a resin layer obtained by applying and drying the photosensitive resin composition to a film.
The cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of the dry film.
The printed wiring board of the present invention is characterized by having the cured product.
The semiconductor device of the present invention is characterized by having the cured product.
The electronic component of the present invention is characterized by having the cured product.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a photosensitive resin composition which can be cured at a low temperature of less than 300 ℃ and can give a cured product having improved chemical resistance and elongation, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, a semiconductor element, a printed wiring board, and an electronic component having the cured product.
Detailed Description
The components contained in the photosensitive resin composition of the present invention will be described in detail below.
[ (A) alkali-soluble resin ]
The photosensitive resin composition of the present invention contains an alkali-soluble resin. The alkali-soluble resin is a resin that is soluble in an alkali aqueous solution as a developer in development after exposure to active energy rays. As the alkali-soluble resin, an alkali-soluble polymer used in a photosensitive resin composition so far can be used. The alkali-soluble polymer has an alkali-soluble group in the molecule, and specifically, an alkali-soluble polymer having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or the like is exemplified. Among them, polymers having a phenolic hydroxyl group or a carboxyl group are preferable, and examples thereof include novolak resins, resol resins, polyimide precursors, polybenzoxazole precursors, and the like. Polyimide precursors and polybenzoxazole precursors are preferred. When these polymers are heated at a predetermined temperature, dehydration ring closure is carried out, and a heat-resistant resin is obtained in the form of polyimide, polybenzoxazole, or a copolymer of both.
The polybenzoxazole precursor is preferably a polyhydroxyamic acid having a repeating structure of the following general formula (4).
(wherein X represents a 4-valent organic group, Y represents a 2-valent organic group, and n is an integer of 1 or more, preferably 10 to 50, more preferably 20 to 40.)
When the polybenzoxazole precursor is synthesized by the above-mentioned synthesis method, in the general formula (4), X is a residue of the dihydroxydiamine and Y is a residue of the dicarboxylic acid.
Examples of the dihydroxydiamines include 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane and 2, 2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane. Among them, 2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane is preferable.
Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 5-t-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalenedicarboxylic acid, 4 ' -dicarboxybiphenyl, 4 ' -dicarboxydiphenyl ether, 4 ' -dicarboxytetraphenylsilane, dicarboxylic acids having an aromatic ring such as bis (4-carboxyphenyl) sulfone, 2-bis (p-carboxyphenyl) propane, 2-bis (4-carboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, and aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, and 1, 3-cyclopentanedicarboxylic acid. Among them, 4' -dicarboxydiphenyl ether is preferable.
In the general formula (4), the 4-valent organic group represented by X may be an aliphatic group or an aromatic group, and is preferably an aromatic group, and more preferably 2 hydroxyl groups and 2 amino groups are located on an aromatic ring in the ortho-position. The number of carbon atoms of the 4-valent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the 4-valent aromatic group include those shown below, but are not limited thereto, and known aromatic groups that can be included in the polybenzoxazole precursor can be selected according to the application.
Among the above aromatic groups, the aromatic group having a valence of 4 is preferably a group shown below.
In the general formula (4), the 2-valent organic group represented by Y may be an aliphatic group or an aromatic group, and is preferably an aromatic group, and is more preferably bonded to the carbonyl group in the general formula (4) on the aromatic ring. The number of carbon atoms of the 2-valent aromatic group is preferably 6 to 30, more preferably 6 to 24. Specific examples of the aromatic group having a valence of 2 include the following groups, but are not limited thereto, and known aromatic groups contained in the polybenzoxazole precursor may be selected according to the application.
(wherein A represents a group selected from the group consisting of a single bond and-CH2-、-O-、-CO-、-S-、-SO2-、-NHCO-、-C(CF3)2-、-C(CH3)2-a group having a valence of 2 in the group consisting. )
Among the aromatic groups, the 2-valent organic group is preferably a group shown below.
The polybenzoxazole precursor may comprise a repeating structure of 2 or more of the above-mentioned polyhydroxyamic acids. In addition, a structure other than the repeating structure of the above-mentioned polyhydroxyamic acid may be included, and for example, a repeating structure of polyamic acid may be included.
The number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 5,000 to 100,000, more preferably 8,000 to 50,000. The number average molecular weight herein is a value measured by Gel Permeation Chromatography (GPC) and converted to standard polystyrene. The polybenzoxazole precursor preferably has a weight average molecular weight (Mw) of 10,000 to 200,000, more preferably 16,000 to 100,000. The weight average molecular weight herein is a value measured by GPC and converted to standard polystyrene. The Mw/Mn is preferably 1 to 5, more preferably 1 to 3.
The polybenzoxazole precursor may be used alone in 1 kind or in combination of 2 or more kinds.
The method for synthesizing the polybenzoxazole precursor is not particularly limited, and the polybenzoxazole precursor can be synthesized by a known method. For example, the compound can be obtained by reacting a dihydroxydiamine as an amine component with a dicarboxylic acid dihalide such as dicarboxylic acid dichloride as an acid component.
(A) The amount of the alkali-soluble resin is preferably 60 to 90% by mass based on the total solid content of the composition. When the content is 60% by mass or more, the adhesiveness and the surface curability are improved. Further, by containing 90 mass% or less, the crosslinking density in the cured product can be prevented from decreasing, and the coating film properties can be improved.
[ (B) photosensitizer ]
The photosensitive resin composition of the present invention contains a photosensitizer. The photosensitizer (B) is not particularly limited, and a photoacid generator, a photopolymerization initiator, and a photobase generator can be used. The photoacid generator is a compound that generates an acid upon irradiation with light such as ultraviolet light or visible light, the photopolymerization initiator is a compound that generates a radical or the like upon irradiation with the same light, and the photobase generator is a compound that generates 1 or more types of basic substances by a change in the molecular structure or a molecular cleavage upon irradiation with the same light. In the present invention, a photoacid generator can be suitably used as the (B) photosensitizer.
Examples of the photoacid generator include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryl di-overlap salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyimide sulfonic acid esters, aromatic sulfonamides, and benzoquinone overlap sulfonic acid esters. The photoacid generator is preferably a dissolution inhibitor. Among them, naphthoquinone diazide compounds are preferable.
Specific examples of the naphthoquinone diazide compound include naphthoquinone diazide adducts of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (e.g., TS533, TS567, TS583, and TS593 available from sanbao chemical research corporation), naphthoquinone diazide adducts of tetrahydroxybenzophenone (e.g., BS550, BS570, BS599 available from sanbao chemical research corporation), and naphthoquinone diazide adducts of 4- {4- [1, 1-bis (4-hydroxyphenyl) ethyl ] - α, α -dimethylbenzyl } phenol (e.g., TKF-428 and TKF-528 available from sanbao chemical research corporation).
Further, as the photopolymerization initiator, conventionally known ones can be used, and for example, an oxime ester type photopolymerization initiator having an oxime ester group, an α -aminoacetophenone type photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator, a titanocene type photopolymerization initiator and the like can be used.
Examples of the oxime ester photopolymerization initiator include CGI-325, IRGACURE OXE01, IRGACURE OXE02, N-1919 and NCI-831 manufactured by ADEKA Ltd.
Specific examples of the α -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, and N, N-dimethylaminoacetophenone, and Omnirad 907, Omnirad 369, Omnirad 379 and the like available from IGM Resins are available.
Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and commercially available products such as Omnirad TPO and Omnirad 819 manufactured by IGM Resins.
Specific examples of the titanocene-based photopolymerization initiator include bis (cyclopentadienyl) -diphenyltitanium, bis (cyclopentadienyl) -dichlorotitanium, bis (cyclopentadienyl) -bis (2,3,4,5, 6-pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2, 6-difluoro-3- (pyrrol-1-yl) phenyl) titanium, and the like. Examples of commercially available products include Omnirad 784 manufactured by IGM Resins.
The photobase generator may be an ionic photobase generator or a nonionic photobase generator, and the ionic photobase generator is preferable because the composition has high sensitivity and is advantageous for forming a pattern film. Examples of the basic substance include secondary amines and tertiary amines.
Examples of the ionic photobase generators include salts of aromatic carboxylic acids and tertiary amines, and ionic PBG manufactured by Wako pure chemical industries, such as WPBG-082, WPBG-167, WPBG-168, WPBG-266, and WPBG-300.
Examples of the nonionic photobase generator include α -aminoacetophenone compounds, oxime ester compounds, and compounds having a substituent such as an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzylcarbamate group, or an alkoxybenzylcarbamate group. As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl-N, N' -diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2-propionyloxy ] piperidine), WPBG-140 (trade name: 1- (anthraquinone-2-yl) ethylimidazolium carboxylate), WPBG-165, and the like, available from Wako pure chemical industries, Ltd.
(B) The photosensitizer may be used alone in 1 kind, or may be used in combination in 2 or more kinds. (B) The amount of the photosensitizer to be blended is preferably 3 to 20% by mass based on the total solid content of the composition.
[ (C) a polyether compound containing 100 to 10,000 polymerized units represented by the general formula (1) ]
The photosensitive resin composition of the present invention comprises (C) a polyether compound comprising 100 to 10,000 polymerized units represented by the general formula (1) (hereinafter, also referred to simply as "(C) polyether compound").
(in the general formula (1), X represents C1-10 alkylene.)
(C) Since the polyether compound has high compatibility with the alkali-soluble resin (a), a high molecular weight material containing 100 or more polymerization units represented by the general formula (1) maintains a uniform morphology even during drying and curing. As a result, the photosensitive resin composition of the present invention containing the polyether compound (C) can have sufficient chemical resistance and mechanical properties even when cured at a low temperature of less than 300 ℃.
Further, the compound represented by the above general formula (1) is hydrophilic, and therefore does not inhibit solubility in an alkaline developing solution. As a result, the photosensitive resin composition of the present invention containing the polyether compound (C) can have resolution equivalent to that of a conventional photosensitive resin composition.
As described above, the photosensitive resin composition of the present invention containing the polyether compound (C) can be cured by heating at a low temperature of less than 300 ℃ without lowering chemical resistance, mechanical properties, and resolution.
By containing 100 or more polymerized units represented by the general formula (1), the photosensitive resin composition of the present invention exhibits sufficient chemical resistance and mechanical properties even when cured at a low temperature of less than 300 ℃. When the number of the polymerization unit is 10,000 or less, the solubility in a solvent is good, and the photosensitive resin composition is suitable for production. More preferably 1,000 to 10,000. By including 1,000 or more of the polymerization units, the contrast ratio, which is the difference in the dissolution rate between the unexposed portions and the exposed portions, is improved, and good resolution is exhibited.
(C) Both ends of the polyether compound are preferably-OR (R represents a hydrogen atom OR an alkylene group having 1 to 10 carbon atoms). Examples of the alkylene group having 1 to 10 carbon atoms which may be used as R include those similar to X in the general formula (1). By making the terminal end the same as the main chain skeleton, the change in compatibility due to the difference in molecular weight can be reduced. (C) Both ends of the polyether compound are preferably-OH. Thereby, good solubility to the alkali developing solution is allowed to be exhibited.
In the general formula (1), examples of the alkylene group having 1 to 10 carbon atoms represented by X include methylene, ethylene, trimethylene and propylene (═ CH)2CH(CH3) -) a straight-chain or branched alkylene group such as tetramethylene group, 1-dimethyltetramethylene group, butylene group, octylene group, decylene group, etc. Among these, alkylene groups having 2 to 4 carbon atoms are preferable, and ethylene groups are more preferable, from the viewpoint of high hydrophilicity and developability with an aqueous alkali solution.
(C) The polyether compound may be a copolymer such as a random copolymer or a block copolymer. Examples of the other polymerization unit include a polymerization unit represented by the general formula (2).
(in the general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms, wherein the same condition as that of X in the general formula (1) is not included.)
In the general formula (2), examples of the alkylene group having 1 to 10 carbon atoms represented by Y include those similar to X in the general formula (1). Among them, a branched alkylene group is preferable, and since the crystallinity is low, the compatibility with the alkali-soluble resin (a) is high, and a more uniform morphology is formed, the photosensitive resin composition of the present invention has more favorable mechanical properties even when cured at a low temperature of less than 300 ℃. Among these, a branched alkylene group having 3 to 5 carbon atoms is more preferable, and a propylene group is further preferable.
(C) The number of the polymerization units represented by the general formula (2) contained in the polyether compound is preferably 1 to 1,000, more preferably 10 to 100. Further, the ratio of the number of the polymerized units represented by the above general formula (2) to the number of the polymerized units represented by the above general formula (1) is preferably 10% or less.
Examples of the other polymerizable units that may be contained in the polyether compound (C) include a polymerizable unit represented by the general formula (3).
(in the general formula (3), Z represents an alkylene group having 1 to 10 carbon atoms having a reactive functional group or a phenyl group in a side chain. examples of the reactive functional group include an aldehyde group, an acyl group, a carbamoyl group, an isocyanate group, an imidazole group, a silanol group, an alkoxysilyl group, a hydroxymethyl group, an alkoxymethyl group, an epoxy group, an oxetanyl group, a vinyl group, an ethynyl group, an allyl group, an acryloyl group, and a methacryloyl group.) when the side chain has the reactive functional group, the side chain reacts with the alkali-soluble resin (A) during curing, and thus a uniform form after curing is maintained. In addition, by including a phenyl group in the side chain, compatibility with the (a) alkali-soluble resin including a large number of aromatic rings can be improved.
(C) The polyether compound preferably contains 1 to 1,000, more preferably 10 to 100 polymerized units represented by the general formula (3).
(C) The proportion of the polymerized units represented by the general formula (1) among the polymerized units contained in the polyether compound is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.
In addition, the proportion of the polymerized unit represented by the general formula (2) in the polymerized units contained in the polyether compound (C) is preferably 1 to 50%, more preferably 3 to 20%, and further preferably 5 to 10%.
In the polymerization units contained in the polyether compound (C), the total ratio of the polymerization units represented by the general formula (1) and the polymerization units represented by the general formula (2) is preferably 80% or more, and more preferably 90% or more. Further, from the viewpoint that the molecular weight occupied by the side chain becomes small, and the side chain interacts with the alkali-soluble resin (a) appropriately to further improve the mechanical properties, and can achieve good solubility in an alkali developing solution, more preferably more than 98%, and particularly preferably 100%.
Specific examples of the polyether compound (C) include polyethylene oxide (PEO) and polypropylene oxide (PPO), an ethylene oxide/propylene oxide copolymer (P (EO/PO)), and a polyether obtained by copolymerizing ethylene oxide having a vinyl group and a phenyl group in a side chain thereof with P (EO/PO).
Among the polyethers, PEO is more hydrophilic than PPO as described above, and PEO is preferable from the viewpoint of developability with an aqueous alkali solution. For the same reason, it is preferable that the ratio of PO to EO in P (EO/PO) is 10% or less.
In addition, as described above, P (EO/PO) has a lower crystallinity than PEO, and therefore P (EO/PO) has a higher compatibility with the alkali-soluble resin (a) than PEO, and forms a more uniform morphology. As a result, P (EO/PO) has better mechanical properties than PEO even when the photosensitive resin composition of the present invention is cured at a low temperature of less than 300 ℃.
(C) The polyether compound is preferably a polymer or copolymer of ethylene oxide or propylene oxide as described above. The polyether compound (C) is more preferably a polyether compound (C) whose polymerization units are composed of only a polymerization unit of the general formula (1) in which X is ethylene and a polymerization unit of the general formula (2) in which Y is propylene.
(C) Examples of the polyether compound include commercially available products such as PEO (Mn: 5,000) manufactured by SIGMA-ALDRICH, PEO (Mn: 8,000, 20,000, 100,000, 200,000) manufactured by Wako pure chemical industries, Ltd., Alkox EP-1010N, CP-A2H, CP-B2, and ZEOSPAN8100, 8030, and 8010 manufactured by Zeon Corporation.
(C) The polyether compound preferably has a number average molecular weight (Mn) of 3,000 to 300,000, more preferably 5,000 to 200,000.
(C) The polyether compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
(C) The amount of the polyether compound to be blended is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, per 100 parts by mass of the alkali-soluble resin (A). Further, the amount is more preferably 7 to 15 parts by mass, and when the photosensitive resin composition is cured at a low temperature by including 7 parts by mass or more, the mechanical properties can be further improved. Further, by containing 15 parts by mass or less, sufficient mixing in the resin composition can be achieved.
(silane coupling agent)
The photosensitive resin composition of the present invention may contain a silane coupling agent. The silane coupling agent is not particularly limited, but a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups are preferable. The silane coupling agent having an arylamino group is more preferable in terms of excellent resolution.
The silane coupling agent having an arylamino group is explained. Examples of the aryl group of the arylamino group include an aromatic hydrocarbon group such as a phenyl group, a tolyl group, a xylyl group, a condensed polycyclic aromatic group such as a naphthyl group, an anthryl group, a phenanthryl group, and an aromatic heterocyclic group such as a thienyl group and an indolyl group.
The silane coupling agent having an arylamino group is preferably a compound having a group represented by the following general formula (5).
(in the formula, R51～R55Each independently represents a hydrogen atom or an organic group. )
In the above general formula (5), R51～R55Preferably a hydrogen atom.
The silane coupling agent having an arylamino group is preferably bonded to an arylamino group through an organic group having 1 to 10 carbon atoms, preferably through an alkylene group having 1 to 10 carbon atoms.
Specific examples of the silane coupling agent having an arylamino group are preferably the compounds shown below.
Next, a silane coupling agent having two or more trialkoxysilyl groups will be described. The trialkoxysilyl groups of the silane coupling agent having two or more trialkoxysilyl groups may be the same or different, and the alkoxy groups of these groups may be the same or different. Examples of the alkoxy group include methoxy, ethoxy, propoxy and butoxy, and among them, methoxy and ethoxy are preferable.
The silane coupling agent having two or more trialkoxysilyl groups is preferably bonded to at least two silicon atoms via an organic group having 1 to 10 carbon atoms, preferably via an alkylene group having 1 to 10 carbon atoms.
Specific examples of the silane coupling agent having two or more trialkoxysilyl groups are preferably the following compounds.
The silane coupling agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Further, a silane coupling agent other than the above-described silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups may be contained.
The amount of the silane coupling agent is preferably 1 to 15% by mass based on the total solid content of the composition. When the amount is 1 to 15% by mass, development residue at the exposed portion can be prevented.
[ sensitizer, adhesion promoter, other ingredients ]
In the photosensitive resin composition of the present invention, a known sensitizer, a known adhesion promoter for improving adhesion to a base material, a crosslinking agent, and the like may be blended in order to further improve the sensitivity within a range not to impair the effects of the present invention. In addition, in order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, other various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, a surfactant, a leveling agent, a plasticizer, fine particles, and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon, and layered silicate. In addition, various colorants, fibers, and the like may be blended in the photosensitive resin composition of the present invention.
[ solvent ]
The solvent used in the photosensitive resin composition of the present invention is not particularly limited as long as it dissolves (a) the alkali-soluble resin, (B) the photosensitizer, (C) the compound represented by the general formula (1) and other additives. Examples thereof include N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of the solvent to be used may be appropriately determined depending on the coating film thickness and viscosity. For example, the resin composition may be used in a range of 50 to 9000 parts by mass per 100 parts by mass of the alkali-soluble resin (A).
The photosensitive resin composition of the present invention is preferably a positive type.
[ Dry film ]
The dry film of the present invention has a resin layer obtained by applying the photosensitive resin composition of the present invention to a carrier film and then drying the applied composition. The resin layer is laminated so as to be in contact with the substrate.
The dry film of the present invention can be produced as follows: the photosensitive resin composition of the present invention is more uniformly applied to a support film by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater, and dried to form the above resin layer, and preferably a cover film is laminated thereon. The cover film and the carrier film may be made of the same film material or different films may be used.
In the dry film of the present invention, any film material of the carrier film and the cover film may be used as the film used in the dry film.
As the carrier film, for example, a thermoplastic film such as a polyester film of polyethylene terephthalate having a thickness of 2 to 150 μm can be used.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, and the adhesive force with the resin layer is preferably smaller than that with the carrier film.
The film thickness of the resin layer on the dry film of the present invention is preferably 100 μm or less, more preferably 5 to 50 μm.
[ cured product ]
The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention in accordance with a predetermined procedure. The pattern film as a cured product thereof can be produced by a known and conventional production method, and for example, in the case of a positive photosensitive resin composition containing a polybenzoxazole precursor as the (a) alkali-soluble resin, it is produced by the following steps.
First, as step 1, a photosensitive resin composition is applied to a substrate and dried, or a resin layer is transferred from a dry film to a substrate, thereby obtaining a coating film. As a method for applying the photosensitive resin composition to the substrate, a method conventionally used for application of a photosensitive resin composition, for example, a method of applying by a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, a method of applying by spraying by a spray coater, an ink jet method, and the like can be used. As a method for drying the coating film, methods such as air drying, heat drying by an oven or a hot plate, and vacuum drying can be used. Further, it is desirable that the drying of the coating film is performed under conditions that do not cause ring closure of the polybenzoxazole precursor in the photosensitive resin composition. Specifically, the drying may be performed by natural drying, air-blowing drying, or heat drying at 70 to 140 ℃ for 1 to 30 minutes. Preferably, drying is carried out on a hot plate for 1 to 20 minutes. Further, vacuum drying may be performed, and in this case, drying may be performed at room temperature for 20 minutes to 1 hour.
The substrate on which the coating film of the photosensitive resin composition is formed is not particularly limited, and a semiconductor substrate such as a silicon wafer, a wiring board, various resins, a metal, and the like can be widely used.
Next, as step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light is light of a wavelength capable of activating the photoacid generator as the (B) photosensitizer. Specifically, the maximum wavelength of the exposure light is preferably in the range of 350 to 410 nm. As described above, by appropriately compounding a sensitizer, the sensitivity can be adjusted. As the exposure device, a contact aligner, a mirror projection, a stepper, a laser direct exposure device, or the like can be used.
Next, as step 3, if necessary, the coating film is heated for a short time to close a part of the polybenzoxazole precursor in the unexposed portion. Here, the closed loop ratio is about 30%. The heating time and the heating temperature may be appropriately changed depending on the type of polybenzoxazole precursor, the thickness of the coating film, and the type of the photosensitizer (B).
Next, as step 4, the coating film is treated with a developer. Thus, the exposed portion of the coating film can be removed, and a patterned film of the photosensitive resin composition of the present invention can be formed.
As the method for development, any method can be selected from conventionally known methods for developing a photoresist, for example, spin coating, paddle method, dipping method with ultrasonic treatment, and the like. Examples of the developer include aqueous solutions of inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, or isopropyl alcohol, or a surfactant may be added to these components. Thereafter, the coating film is washed with a washing liquid as necessary to obtain a pattern film. As the rinse solution, distilled water, methanol, ethanol, isopropyl alcohol, or the like can be used alone or in combination. In addition, as the developer, the above-mentioned solvent can be used.
Thereafter, as step 5, the pattern film is heated to obtain a cured coating film (cured product). By this heating, the polybenzoxazole precursor is ring-closed to obtain polybenzoxazole. As for the heating temperature, it may be appropriately set so that the pattern film of the photosensitive resin composition can be cured. For example, the heating is performed in an inert gas at 150 ℃ or higher and lower than 300 ℃ for about 5 to 120 minutes. The more preferable range of the heating temperature is 180 to 250 ℃. Since the photosensitive resin composition of the present invention contains (C) a polyether compound, cyclization is promoted, and a heating temperature of less than 300 ℃ can be used. The heating is performed by using, for example, a hot plate, an oven, or an oven of an elevated temperature type capable of setting a temperature program. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.
When the photosensitive resin composition of the present invention is a negative photosensitive resin composition, a photopolymerization initiator or a photobase generator is used as the photosensitizer (B) in place of a photoacid generator, and the unexposed portion of the coating film is removed by treating the coating film with a developer in step 4, whereby a pattern film of the photosensitive resin composition of the present invention can be formed.
The application of the photosensitive resin composition of the present invention is not particularly limited, and the photosensitive resin composition is suitably used as a coating material, a printing ink, an adhesive, or a material for forming a display device, a semiconductor device, an electronic component, an optical component, or a building material, for example. Specifically, the material for forming a display device can be used as a material for forming a layer or an image forming material for a color filter, a thin film for a flexible display, a resist material, an alignment film, or the like. The material for forming a semiconductor device can be used for a resist material, a layer forming material such as a buffer coating film, or the like. Furthermore, as a material for forming electronic components, a sealing material or a layer forming material can be used for a printed wiring board, an interlayer insulating film, a wiring coating film, and the like. Further, as a material for forming an optical component, as an optical material or a layer forming material, the material can be used for a hologram, an optical waveguide, an optical circuit component, an antireflection film, and the like. Further, the resin composition can be used as a building material for paints, coating agents, and the like.
The photosensitive resin composition of the present invention is mainly used as a pattern forming material, and a pattern film formed therefrom, for example, a permanent film formed of polybenzoxazole or the like, functions as a component imparting heat resistance and insulation properties, and is therefore particularly suitable for use 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 devices having a bump structure, an interlayer insulating film for multilayer circuits, an insulating material for passive components, a solder resist, a protective film for printed wiring boards such as a cover film, and a liquid crystal alignment film or the like of a semiconductor device, a display device, and a light-emitting device. Particularly, it is suitably used for an insulating film or the like in contact with a copper wiring or an aluminum wiring.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the following, all of the "parts" and "%" are based on mass unless otherwise specified.
(Synthesis of Polybenzoxazole (PBO) precursor)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 212g of N-methylpyrrolidone was charged, and 28.00g (76.5mmol) of bis (3-amino-4-hydroxyamidophenyl) hexafluoropropane was dissolved with stirring. Thereafter, the flask was immersed in an ice bath, and while maintaining the flask at 0 to 5 ℃, 25.00g (83.2mmol) of 4, 4-diphenylether dicarboxylic acid dichloride was added as a solid in 5g portions over 30 minutes, and stirred in the ice bath for 30 minutes. Thereafter, stirring was continued at room temperature for 5 hours. The stirred solution was poured into 1L of ion-exchanged water (resistivity value: 18.2 M.OMEGA.. multidot.cm), and a precipitate was collected. Thereafter, the obtained solid was dissolved in 420mL of acetone and charged into 1L of ion-exchanged water. The precipitated solid was collected and dried under reduced pressure to obtain Polybenzoxazole (PBO) precursor a-1 having a carboxyl terminal and having a repeating structure shown below. The polybenzoxazole precursor A-1 had a number average molecular weight (Mn) of 12,900, a weight average molecular weight (Mw) of 29,300, and Mw/Mn of 2.28.
(examples 1 to 9)
To 100 parts by mass of the polybenzoxazole precursor synthesized above, 10 parts by mass of naphthoquinone diazide compound B-1 (TKF-428, manufactured by Sanbao chemical Co., Ltd.) as a photosensitizer (B), 7 parts by mass of silane coupling agent having arylamino group (KBM-573, manufactured by Shin-Etsu Silicones) as a silane coupling agent, and polyether compounds of C-1 to C-4 shown below were mixed, and then γ -butyrolactone (GBL) was added so that the benzoxazole precursor became 30% by mass to prepare varnishes, thereby preparing photosensitive resin compositions of examples 1 to 9. Incidentally, PEO (Mn: 5,000) manufactured by SIGMA-ALDRICH and PEO (Mn: 8,000, 20,000, 100,000, 200,000) manufactured by Wako pure chemical industries, Ltd, were used as C-1, Alkox EP-1010N (random copolymer of ethylene oxide and propylene oxide, m: N: 12: 1, Mn: about 10 ten thousand) manufactured by Minghua chemical Co., Ltd, were used as C-3, Alkox CP-A2H (random copolymer of allyl glycidyl ether, ethylene oxide, and propylene oxide, l: m: N: 96: 1: 3, Mn: about 8) manufactured by Minghua chemical Co., Ltd, were used as C-4, and Alkox CP-B2 (random copolymer of ethylene oxide and phenyl glycidyl ether, N: m: 1: 2, Mn: 97: about 10) manufactured by Minghua chemical Co., Ltd, was used as C-1.
Comparative examples 1 to 6
The photosensitive resin composition of comparative example 1 was prepared in the same manner as in example 1, except that the polyether compound (C) of C-1 was not blended as in comparative example 1.
Photosensitive resin compositions of comparative examples 2 to 6 were prepared in the same manner as in examples 1 to 5 except that melamine-based or urea-based crosslinking agents C-5 to C-8 shown below were added in place of the polyether compounds C-1 to C-4 (C) in comparative examples 2 to 6.
The photosensitive resin compositions of examples 1 to 9 and comparative examples 1 to 6 thus prepared were evaluated for resolution, chemical resistance, and elongation at break. The evaluation method is as follows.
(method of producing dried coating film for evaluation)
The photosensitive resin composition was applied to a silicon substrate by a spin coater, and dried at 120 ℃ for 3 minutes by a hot plate to obtain a dried coating film of the photosensitive resin composition.
(evaluation of chemical resistance)
The dried coating film obtained above was heated at 240 ℃ for 1 hour on a hot plate, and the resulting cured product was immersed in gamma-butyrolactone (GBL) for 10 minutes to evaluate the presence or absence of a change in film thickness and cracks. The chemical resistance in tables 1 and 2 was evaluated by the following criteria.
Variation of film thickness
O: the variation of the film thickness is less than +/-1 percent
And (delta): film thickness change was ± (1% or more and less than 5%)
X: the film thickness variation is more than +/-5 percent
Crack(s)
O: no cracks in 1cm divisions
And (delta): 1 or more and less than 10 cracks in a 1cm zone
X: more than 10 cracks in 1cm subarea
(evaluation of elongation at Break)
The dried coating film obtained above was heated at 240 ℃ for 1 hour on a hot plate, and after passing through a PCT apparatus (HAST SYSTEM TPC-412MD, manufactured by ESCECCorp. at 121 ℃ C., under 0.2MPa for 168 hours, the cured film having a peel thickness of 30 μm was cut into a length of 50 mm. times.a width of 5mm, and subjected to a tensile test by "EZ-SX", manufactured by Shimadzu corporation. The distance between the clamps was 30mm, and the drawing speed was 3mm/mm, and 7 measurements were made, and the average of the first 3 of them was taken as the elongation at break.
The following criteria were used for the evaluation of the elongation at break in tables 1 and 2.
Very good: over 20 percent
O: more than 15 percent and less than 20 percent
And (delta): more than 10 percent and less than 15 percent
X: less than 10 percent
Table 1 and table 2 show the heating temperature during heating, and also show the chemical resistance and the results of the evaluation of the elongation at break.
[ Table 1]
[ Table 2]
As is clear from tables 1 and 2, examples 1 to 9 containing (C) a polyether compound having 100 to 10,000 polymerized units are sufficiently curable at a low temperature such as 240 ℃ and exhibit sufficient chemical resistance and elongation at break. Further, example 6 in which the compound containing C-2 was used as the (C) polyether compound was able to further improve the elongation at break. In examples 1 to 9, the resolution was the same as that of the conventional photosensitive resin composition.
In contrast, comparative example 1 was not sufficiently cured at a heating temperature of 240 ℃ because the polyether compound (C) was not blended. In addition, comparative examples 2 to 5, which contain additives other than the polyether compound (C) as a crosslinking agent, did not have sufficient chemical resistance. Further, in comparative example 6, the chemical resistance was improved by increasing the amount of the melamine-based crosslinking agent, but the elongation at break was lower than that of the conventional photosensitive resin composition.
Claims (10)
1. A photosensitive resin composition, comprising: (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a polyether compound comprising 100 to 10000 polymerized units represented by the general formula (1),
in the general formula (1), X represents an alkylene group having 1 to 10 carbon atoms.
2. The photosensitive resin composition according to claim 1, wherein the polyether compound (C) further comprises 1 to 1000 polymerized units represented by the general formula (2),
in the general formula (2), Y represents an alkylene group having 1 to 10 carbon atoms, and the same as X in the general formula (1) is not included.
3. The photosensitive resin composition according to claim 1, wherein the polyether compound (C) further comprises 1 to 1000 polymerized units represented by the general formula (3),
in the general formula (3), Z represents an alkylene group having 1 to 10 carbon atoms and having a reactive functional group or a phenyl group in a side chain.
4. The photosensitive resin composition according to claim 1, comprising a polybenzoxazole precursor as the (a) alkali-soluble resin.
5. The photosensitive resin composition according to claim 1, wherein a naphthoquinone diazide compound is contained as the (B) photosensitizer.
6. A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 1 to a film and drying the applied film.
7. A cured product obtained by curing the resin layer of the photosensitive resin composition according to any one of claims 1 to 5 or the dry film according to claim 6.
8. A printed wiring board comprising the cured product according to claim 7.
9. A semiconductor device comprising the cured product according to claim 7.
10. An electronic component comprising the cured product according to claim 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018-065814 | 2018-03-29 | ||
| JP2018065814 | 2018-03-29 | ||
| PCT/JP2019/010709 WO2019188379A1 (en) | 2018-03-29 | 2019-03-14 | Photosensitive resin composition, dry film, cured product, printed wiring board, and semiconductor element |
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| CN111819493A true CN111819493A (en) | 2020-10-23 |
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| JP (1) | JP7360380B2 (en) |
| KR (1) | KR20200138252A (en) |
| CN (1) | CN111819493A (en) |
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| WO (1) | WO2019188379A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001109144A (en) * | 1999-10-06 | 2001-04-20 | Shipley Far East Ltd | Positive type photoresist composition |
| JP4046563B2 (en) | 2002-01-25 | 2008-02-13 | 旭化成エレクトロニクス株式会社 | High heat-resistant photosensitive resin composition |
| JP2009069589A (en) * | 2007-09-14 | 2009-04-02 | Fujifilm Corp | Image forming method |
| KR102159761B1 (en) * | 2013-08-12 | 2020-09-24 | 미쯔비시 케미컬 주식회사 | Adhesive agent composition, adhesive agent composition for polarizing plate, adhesive agent for polarizing plate, and polarizing plate manufactured using said adhesive agent |
| JP2018031799A (en) * | 2014-12-26 | 2018-03-01 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
| JP6669742B2 (en) * | 2015-06-09 | 2020-03-18 | 旭化成株式会社 | Aqueous resin composition for touch panel, transfer film and cured film laminate, method for producing resin pattern, and touch panel display device |
| US10533287B2 (en) * | 2015-09-29 | 2020-01-14 | Kuraray Co., Ltd. | Dispersant for carbon fibers, carbon fiber dispersion composition, and method for manufacturing carbon fiber sheet |
| US10324376B2 (en) * | 2015-09-30 | 2019-06-18 | Toray Industries, Inc. | Negative type colored photosensitive resin composition, cured film, element, and display device |
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| TWI791801B (en) | 2023-02-11 |
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| KR20200138252A (en) | 2020-12-09 |
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Application publication date: 20201023 |