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WO2009151012A1 - Résine polyamide, composition de résine photosensible, procédé de formation de motif en relief durci, et dispositif semi-conducteur - Google Patents

Résine polyamide, composition de résine photosensible, procédé de formation de motif en relief durci, et dispositif semi-conducteur Download PDF

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Publication number
WO2009151012A1
WO2009151012A1 PCT/JP2009/060380 JP2009060380W WO2009151012A1 WO 2009151012 A1 WO2009151012 A1 WO 2009151012A1 JP 2009060380 W JP2009060380 W JP 2009060380W WO 2009151012 A1 WO2009151012 A1 WO 2009151012A1
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WIPO (PCT)
Prior art keywords
group
resin composition
carbon atoms
polyamide resin
photosensitive resin
Prior art date
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Ceased
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PCT/JP2009/060380
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English (en)
Japanese (ja)
Inventor
正志 木村
隆行 金田
基博 丹羽
竜也 平田
正樹 本多
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Asahi Kasei Corp
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Asahi Kasei E Materials Corp
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Priority to CN2009801005599A priority Critical patent/CN101809064B/zh
Priority to KR1020107006824A priority patent/KR101187613B1/ko
Priority to JP2010516837A priority patent/JP5351155B2/ja
Publication of WO2009151012A1 publication Critical patent/WO2009151012A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0277—Electrolithographic processes

Definitions

  • the present invention relates to a polyamide that can be used for an insulating material for electronic parts, a surface protective film for semiconductor devices, an interlayer insulating film, a heat-resistant coating film such as an alpha ray shielding film, and a semiconductor device equipped with an image sensor, micromachine, or microactuator.
  • the present invention relates to a resin, a photosensitive resin composition containing the polyamide resin, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern. More specifically, the present invention is a novel photosensitivity that exhibits excellent photosensitivity during ultraviolet exposure, such as excellent heat resistance, chemical resistance, mechanical properties, and low residual stress characteristics even under heat curing conditions of 200 ° C. or lower.
  • the present invention relates to a polyamide resin, a photosensitive resin composition containing the polyamide resin, and a semiconductor device manufactured using the photosensitive resin composition.
  • Polyimide resins having excellent heat resistance, electrical properties, and mechanical properties are widely used for insulating materials for electronic parts and surface protection films, interlayer insulation films, and ⁇ -ray shielding films for semiconductor devices.
  • This resin is usually provided in the form of a photosensitive polyimide precursor composition, which is applied to a substrate, irradiated with an actinic ray (exposure) through a desired patterning mask, developed, and heat-cured (heat By performing the (imidization) treatment, a relief pattern made of a heat-resistant polyimide resin can be easily formed (see, for example, Patent Document 1 below).
  • Patent Document 3 discloses a polyamide in which a photosensitive group is directly bonded to a resin skeleton via an amide group
  • Patent Document 4 discloses a polyimide amide.
  • the problems to be solved by the present invention are excellent in sensitivity and resolution. For example, even when a resin film is formed under a low-temperature heat-curing condition such as 200 ° C. or less, film characteristics excellent in chemical resistance are imparted to the resin film. It is to provide a polyamide resin and a photosensitive resin composition. Furthermore, it is a problem to be solved by the present invention to provide a method for forming a cured relief pattern using the photosensitive resin composition and a semiconductor device having a cured relief pattern formed by the method.
  • the present inventors have found that the above problems can be solved by producing a photosensitive resin composition based on a polyamide produced from a specific raw material.
  • the invention has been completed. Specifically, the present invention is as follows [1] to [16]:
  • R 1 is represented by the following formula (4): ⁇ In the formula, R 2 is a C 4-19 aliphatic group having at least one radical-polymerizable unsaturated bond group. ⁇ , The polyamide resin according to any one of [1] to [3] above.
  • the above W, X, and Y are each independently a group selected from the group consisting of an aromatic group, an alicyclic group, an aliphatic group, a siloxane group, and a group of a composite structure thereof.
  • the polyamide resin according to any one of [3].
  • a photosensitive resin composition comprising (A) 100 parts by mass of the polyamide resin according to any one of [1] to [6], and (B) 0.5 to 20 parts by mass of a photopolymerization initiator.
  • a heat-crosslinkable compound is further contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polyamide resin (A), and the (D) heat-crosslinkable compound is a polyamide (A)
  • a photosensitive resin composition solution comprising the photosensitive resin composition according to any one of [7] to [13] above and a solvent.
  • the photosensitive resin composition according to any one of the above [7] to [13] or the photosensitive resin composition solution according to the above [14] is applied on a substrate, and the photosensitive resin composition is applied.
  • the polyamide resin of the present invention and the photosensitive resin composition containing the same can provide a resin film exhibiting excellent chemical resistance even under low temperature heat curing conditions such as 200 ° C. or lower.
  • the present invention also provides a method for forming a cured relief pattern excellent in chemical resistance using the photosensitive resin composition, and a semiconductor device having a cured relief pattern formed by the method.
  • the present invention provides the following formula (1):
  • X is a trivalent organic group having 6 to 15 carbon atoms
  • m 0 or 2
  • R 1 is a radically polymerizable unsaturated bond group having 5 to 20 carbon atoms, which may contain atoms other than carbon. It is an aliphatic group having at least one. Are included so that the number of repetitions is in the range of 2 to 150 and the number of repetitions is in the range of 80 to 100% of the total number of all the structural units constituting the polyamide resin. provide.
  • the number of repeating structural units represented by the above formula (1) in one molecule of the polyamide resin is 2 to 150, and if it is 2 or more, the requirements as a polymer expected by the present invention are satisfied. If it is 150 or less, it is preferable from the viewpoints of solubility in a diluting solvent when preparing a photosensitive resin composition, rapidity during development processing, and the like.
  • the number of repeating units of the structural unit represented by the above formula (1) is more preferably 2 to 100. In the present specification, the number of repeating structural units means the number of the structural units present in one molecule, and the structural units may be repeated continuously or through other structural units. Also good.
  • the ratio of the number of repeating structural units represented by the above formula (1) in the total number of all structural units constituting the polyamide resin is in the range of 80 to 100%.
  • the ratio is 80% or more, the photosensitive properties of the coating film composed of the photosensitive resin composition of the present invention can be improved to the extent expected by the present invention, and further, the mechanical properties after heat curing of the coating film and The heat resistance and chemical resistance can also be improved to the extent expected by the present invention.
  • the ratio is preferably 85% or more.
  • the structural unit of the polyamide resin may be only the structural unit represented by the above formula (1) from the viewpoint of photosensitive characteristics, heat resistance, and chemical resistance (that is, the ratio is 100%), but in the process of forming a semiconductor element.
  • the polyamide resin has a structural unit other than the structural unit represented by the above (1) for the purpose of, for example, further improving the adhesion with various structural materials in contact with it or imparting various properties as desired.
  • the ratio is 20% or less, preferably 15% or less.
  • the repeating number of the structural unit represented by the formula (1) is 2 and 3, the repeating number is 100% of the total number of all the structural units constituting the polyamide resin.
  • the present invention provides the following formula (2):
  • X is a trivalent organic group having 6 to 15 carbon atoms
  • m 0 or 2
  • W is a divalent organic group having 6 to 15 carbon atoms
  • k is an integer of 1 or more
  • R 1 is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and has at least one radical-polymerizable unsaturated bond group.
  • the number of repetitions n in the above formula (2) is 80% or more of the total number of all structural units constituting the polyamide resin.
  • the arrangement of the structure with the repetition number n and the structure with the repetition number k may be random or block.
  • K in the formula (2) is an integer of 1 or more, and (n + k) is an integer of 5 to 150 at the same time.
  • k is 1 or more, the effect of copolymerizing various structures represented by the number k of repetitions can be obtained.
  • (n + k) is 5 or more, the requirements as a polymer expected by the present invention are satisfied, and when it is 150 or less, solubility in a diluting solvent when forming a photosensitive resin composition, or during development processing It is preferable in terms of rapidity.
  • (N + k) is preferably 5 to 100.
  • the ratio of the number of structural units having the repeating number n in the above formula (2) (that is, n) is 80% or more. If the ratio is 80% or more, the photosensitive properties of the coating film made of the photosensitive resin composition of the present invention can be improved to the extent expected by the present invention, and the machine after the coating film is heat-cured. The physical properties, heat resistance, and chemical resistance can also be improved to the extent expected by the present invention.
  • the ratio is preferably 85% or more.
  • the ratio of the number of structural units having the number k of repetitions in the above formula (2) (that is, k) in the total number of all structural units constituting the polyamide resin is 20% or less. If the ratio is 20% or less, the excellent photosensitivity, mechanical properties, heat resistance, and chemical resistance of the present invention are ensured, and at the same time, the adhesion to various constituent materials that are in contact with each other in the process of forming a semiconductor element is improved. In addition to further improvements, various characteristics can be imparted as desired.
  • the ratio is preferably 15% or less.
  • the polyamide resin in this embodiment may have only the structure represented by the above formula (2) as a structural unit from the viewpoint of achieving the photosensitive properties and mechanical properties, heat resistance, and chemical resistance that are the object of the present invention, You may have structural units other than the structure represented by the said Formula (2).
  • the molecular chain terminal is a carboxyl group derived from a dicarboxylic acid containing a trivalent organic group represented by X Or an amino group derived from a diamine containing a divalent or tetravalent organic group represented by Y, but various chemical modifications of the carboxyl group (for example, ester, amide, etc.) and various amino groups It may be a chemically modified product (for example, amide, urethane, imide, etc.).
  • the present invention provides the following formula (3):
  • X is a trivalent organic group having 6 to 15 carbon atoms
  • m 0 or 2
  • W is a divalent organic group having 6 to 15 carbon atoms
  • l is 0 or an integer of 1 or more
  • ( n + 1) is an integer of 2 to 150
  • R 1 is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and which has at least one radical-polymerizable unsaturated bond group.
  • ⁇ Is provided as a structural unit, and a polyamide resin having a repeating number n in the above formula (3) in the range of 80 to 100% of all structural units constituting the polyamide resin is provided.
  • the arrangement of the structure with the repetition number n and the structure with the repetition number l may be random or block.
  • (n + 1) is 2 to 150, and if it is 2 or more, the requirements as a polymer expected by the present invention are satisfied, and if it is 150 or less, a photosensitive resin composition is obtained. Is preferable in terms of solubility in a diluting solvent and rapidity during development processing.
  • the repeating number of the structural unit represented by the above formula (3) is preferably 2 to 100.
  • the ratio of the number of repeating units represented by repeating unit n out of the total number of all constituting units constituting the polyamide resin is in the range of 80 to 100%.
  • the ratio is 80% or more, the photosensitive properties of the coating film composed of the photosensitive resin composition of the present invention can be improved to the extent expected by the present invention, and further, the mechanical properties after heat curing of the coating film and The heat resistance and chemical resistance can also be improved to the extent expected by the present invention.
  • the ratio is preferably 85% or more.
  • the constitutional unit of the polyamide resin may be only the constitutional unit represented by the repeating unit n (the ratio of n is 100%) from the viewpoint of photosensitive characteristics, heat resistance, and chemical resistance, but is in contact in the process of forming a semiconductor element.
  • a structural unit represented by a repeating unit 1 for the purpose of further improving the adhesion with various structural materials or imparting various properties as desired, in which case the above ratio is It is 20% or less, and preferably 15% or less.
  • the constitutional unit represented by the repeating unit 1 is 20% or less of the total number of all constitutional units, various properties can be obtained as desired while ensuring the photosensitive properties, mechanical properties, heat resistance, and chemical resistance achieved in the present invention. It is possible to impart the characteristics of When (n + 1) is 2 to 4, the structural unit represented by the repeating unit n is 100% of the total number of all structural units constituting the polyamide resin.
  • the molecular chain terminal of the polyamide resin in this embodiment is a carboxyl group derived from a dicarboxylic acid containing a trivalent organic group represented by X, a carboxyl group derived from a dicarboxylic acid containing a divalent organic group represented by W, or Y Is a diamine-derived amino group containing a divalent or tetravalent organic group represented by the formula, but various chemical modifications of the carboxyl group (for example, ester, amide, etc.) and various chemical modifications of the amino group (For example, an amide body, a urethane body, an imide body, etc.) may be sufficient.
  • R 1 is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and has at least one radical-polymerizable unsaturated bond group. is there.
  • R 1 is represented by the following formula (4) from the viewpoint of photosensitive characteristics and chemical resistance:
  • R 2 is a C 4-19 aliphatic group having at least one radical-polymerizable unsaturated bond group. ⁇ Is preferable. From the viewpoint of further improving the photosensitive characteristics, R 1 is preferably a group having at least one (meth) acryloyloxymethyl group.
  • the trivalent organic group represented by X is a trivalent organic group having 6 to 15 carbon atoms from the viewpoint of photosensitive properties, mechanical properties, heat resistance, chemical resistance, and the like. It is a group.
  • the divalent or tetravalent organic group represented by Y is an organic group having 6 to 35 carbon atoms from the viewpoint of photosensitive properties, mechanical properties, heat resistance, chemical resistance, and the like. is there.
  • the divalent organic group represented by W is a divalent organic group having 6 to 15 carbon atoms from the viewpoint of photosensitive properties, heat resistance, heat resistance, chemical resistance, and the like. It is a group. W is a structure obtained by removing two carboxyl group-derived moieties from the structure of dicarboxylic acid or its derivative.
  • the above W, X and Y are each independently an aromatic group, alicyclic group, aliphatic group, siloxane group. And a group selected from the group consisting of groups of these complex structures.
  • X is the following structure:
  • the aromatic group is more preferably an aromatic group selected from the group consisting of groups represented by the formula (1), and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an amino group-substituted isophthalic acid structure.
  • Y represents a cyclic organic group having 1 to 4 aromatic or aliphatic rings which may be substituted, or an aliphatic group or siloxane group having no cyclic structure. It is more preferable.
  • preferred examples of the cyclic organic group include the following aromatic groups or alicyclic groups:
  • each A is independently one group selected from the group consisting of a hydroxyl group, a methyl group, an ethyl group, a propyl group, and a butyl group.
  • p and q are each independently an integer of 0 to 3
  • r is an integer of 0 to 8
  • s and t are each independently an integer of 0 to 10
  • B is a methyl group, ethyl Group, propyl group, butyl group or isomers thereof.
  • p and q each represent the number of repeating methylene chains
  • r, s and t each represent the number of substituents on the ring of the substituent B
  • B represents a substituent on the ring, particularly 1 to 4 hydrocarbon groups are represented.
  • aliphatic group or siloxane group having no cyclic structure include the following:
  • a is an integer of 2 to 12
  • b is an integer of 1 to 3
  • c is an integer of 1 to 20
  • R 3 and R 4 each independently represent 1 to 3 carbon atoms. Or an optionally substituted phenyl group. ⁇ Group.
  • W in formulas (2) and (3) is preferably an aromatic group, an aliphatic group or an alicyclic group, respectively.
  • Preferred aromatic groups include the following groups:
  • the polyamide resin of the present invention can be synthesized, for example, as follows.
  • a compound having a trivalent aromatic group X for example, phthalic acid substituted with an amino group, substituted with an amino group 1 mol or more of a compound selected from the group consisting of terephthalic acid substituted with an amino group and terephthalic acid substituted with an amino group (hereinafter referred to as “phthalic acid compound”), and one or more types that react with an amino group A compound obtained by reacting with 1 mol of a compound and modifying and sealing the amino group of the phthalic acid compound with one or more groups containing a radical polymerizable unsaturated bond described later (hereinafter referred to as “phthalic acid compound sealing”). Body)).
  • phthalic acid compound sealing one or more types that react with an amino group A compound obtained by reacting with 1 mol of a compound and modifying and sealing the amino group of the phthalic acid compound with one or more groups containing a radical polymerizable unsaturated bond described later
  • a structure in which a phthalic acid compound is sealed with a group containing the above radical polymerizable unsaturated bond can impart negative photosensitivity (that is, photocuring property) to the polyamide resin.
  • the group containing a radically polymerizable unsaturated bond is preferably an aliphatic group having 5 to 20 carbon atoms having a radically polymerizable unsaturated bond group from the viewpoint of photosensitive properties and chemical resistance, and methacryloyloxymethyl. Particularly preferred are aliphatic groups containing groups and / or acryloyloxymethyl groups.
  • the encapsulated phthalic acid compound includes an aliphatic acid chloride having 5 to 20 carbon atoms, an aliphatic isocyanate, or an aliphatic epoxy compound having at least one amino group of the phthalic acid compound and a radical polymerizable unsaturated bond group. It can obtain by making it react with.
  • Suitable aliphatic acid chlorides include 2-[(meth) acryloyloxy] acetyl chloride, 3-[(meth) acryloyloxy] propionyl chloride, 2-[(meth) acryloyloxy] ethyl chloroformate, 3- [ (Meth) acryloyloxypropyl] chloroformate and the like.
  • Suitable aliphatic isocyanates include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, 2- [2- (meth) acryloyloxyethoxy] ethyl isocyanate] and the like Is mentioned.
  • Suitable aliphatic epoxy compounds include glycidyl (meth) acrylate and the like. These may be used alone or in combination of two or more. It is particularly preferred to use 2-methacryloyloxyethyl isocyanate.
  • the phthalic acid compound encapsulant one in which the phthalic acid compound is 5-aminoisophthalic acid is preferable because a polyamide resin having excellent photosensitivity and film characteristics after heat curing can be obtained. .
  • the sealing reaction proceeds by stirring and dissolving and mixing the phthalic acid compound and the sealing agent in a reaction solvent in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate. be able to.
  • a basic catalyst such as pyridine
  • a tin-based catalyst such as di-n-butyltin dilaurate.
  • the reaction solvent is preferably one that completely dissolves the product phthalic acid compound encapsulant, such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide. , Tetramethylurea, gamma butyrolactone and the like.
  • reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons and hydrocarbons, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate.
  • hydrogen chloride may be produced as a by-product during the sealing reaction.
  • the product is once again re-precipitated with water, washed with water and dried, or passed through a column filled with ion exchange resin to reduce or reduce ionic components. It is preferable to carry out.
  • polyamide resin Secondly, the phthalic acid compound encapsulated body and a diamine compound having a divalent or tetravalent organic group Y (a group corresponding to Y in each of the above formulas) are mixed with pyridine, triethylamine or the like.
  • the polyamide resin of the present invention can be obtained by mixing in an appropriate solvent in the presence of a basic catalyst and subjecting it to amide polycondensation.
  • a part of the sealed phthalic acid compound can be used in combination with a dicarboxylic acid having a divalent organic group W (a group corresponding to W in the above formulas).
  • W a group corresponding to W in the above formulas.
  • the ratio of the number of structures derived from the sealed phthalic acid compound in the total number of all structural units of the polyamide resin is 80% or more and 100% or less.
  • a dicarboxylic acid component (a phthalic acid compound encapsulated body and a dicarboxylic acid having a divalent organic group W; the same shall apply hereinafter) was converted into a symmetric polyacid anhydride using a dehydrating condensing agent.
  • a method of mixing with a diamine compound later a method of mixing a dicarboxylic acid component with an acid chloride by a known method and then mixing with a diamine compound, and reacting a dicarboxylic acid component with an active esterifying agent in the presence of a dehydrating condensing agent
  • a method of mixing the product with a diamine compound after esterification is exemplified.
  • Preferred dehydration condensing agents include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1′-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples thereof include N′-disuccinimidyl carbonate.
  • chlorinating agent examples include thionyl chloride.
  • active esterifying agents include N-hydroxysuccinimide, 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2-cyanoacetic acid ethyl, 2-hydroxyimino- And 2-cyanoacetamide.
  • dicarboxylic acid having a divalent organic group W examples include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-diphenyl ether dicarboxylic acid, 3,4′-diphenyl ether dicarboxylic acid, 3,3′-diphenyl ether dicarboxylic acid, 4 , 4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 3,3'-benzophenone Dicarboxylic acid, 4,4'-hexafluoroisopropylidene dibenzoic acid, 4,4'-dicarboxydiphenylamide, 1,4-phenylenediethanic acid, 1,1-bis (4-carboxyphenyl) -1-phenyl -2,2,2-trifluor
  • the diamine compound having an organic group Y is at least one diamine selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a siloxane diamine compound.
  • a compound is preferable, and a plurality of types can be used in combination as desired.
  • aromatic diamine compound examples include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'- Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-di
  • diamine compounds in which a hydrogen atom on the benzene ring is substituted include 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4′-diaminobiphenyl and the like.
  • Aromatic bisaminophenol compounds include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminodiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) Propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'- Aminodiphenyl ether, 4,4′-dihydroxy-3,3′-di
  • alicyclic diamine compounds include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 1,5 -Diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2 , 5-diethylcyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2- (3-aminocyclopentyl) -2-propylamine, mensendiamine, isophoronediamine, norbornane Diamine, 1-
  • linear aliphatic diamine compounds examples include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane.
  • Hydrocarbon-type diamines such as 2- (2-aminoethoxy) ethylamine, 2,2 ′-(ethylenedioxy) diethylamine, and bis [2- (2-aminoethoxy) ethyl] ether Can be mentioned.
  • siloxane diamine compound examples include dimethyl (poly) siloxane diamine, for example, trade names PAM-E, KF-8010, and X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.
  • reaction solvent a solvent that completely dissolves the polymer to be produced is preferable.
  • a solvent that completely dissolves the polymer to be produced is preferable.
  • ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may be used as a reaction solvent.
  • the precipitate derived from the dehydrating condensing agent that has precipitated in the reaction solution is filtered off as necessary.
  • a poor polyamide solvent such as water, an aliphatic lower alcohol or a mixture thereof is added to the reaction solution to precipitate the polyamide.
  • the precipitated polyamide is redissolved in a solvent and purified by repeating the reprecipitation precipitation, followed by vacuum drying to isolate the target polyamide.
  • this polyamide solution may be passed through a column packed with an ion exchange resin to remove ionic impurities.
  • the weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”) of the polyamide resin of the present invention is preferably 7,000 to 70,000, and 10,000 to 50,000. Is more preferable.
  • the weight average molecular weight in terms of polystyrene is 7,000 or more, the basic physical properties of the cured relief pattern are good.
  • the polystyrene conversion weight average molecular weight is 70,000 or less, the development solubility at the time of forming a relief pattern is good.
  • Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as GPC eluents.
  • a weight average molecular weight value is calculated
  • the standard monodisperse polystyrene is recommended to be selected from Showa Denko's organic solvent standard sample STANDARD SM-105.
  • the present invention relates to a photosensitive resin composition
  • a photosensitive resin composition comprising (A) 100 parts by mass of the above-described polyamide resin of the present invention (hereinafter also referred to as (A) polyamide resin) and (B) 0.5-20 parts by mass of a photopolymerization initiator. Things are also provided. Specific embodiments of the (A) polyamide resin that can be used in the photosensitive resin composition of the present invention are as described above. In the photosensitive resin composition of the present invention, from the viewpoint of imparting photosensitive characteristics, the (A) polyamide resin and (B) photopolymerization initiator are used in combination.
  • Photopolymerization initiator any conventionally known compound can be used as a photopolymerization initiator for polyamide.
  • any conventionally known compound can be used as a photopolymerization initiator for polyamide.
  • Benzophenone benzophenone derivatives such as methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, etc.
  • the oxime [6] is more preferable particularly from the viewpoint of photosensitivity.
  • the blending amount of the (B) photopolymerization initiator with respect to 100 parts by mass of the (A) polyamide resin is preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass.
  • radicals sufficient to allow photoradical polymerization to proceed sufficiently are supplied during exposure, ensuring sufficiently good photosensitivity for practical use, and a relief pattern suitable for practical use. Can be obtained.
  • the said compounding quantity is 20 mass parts or less
  • coated since an exposure light beam can be made to reach
  • the photosensitive resin composition of the present invention comprises (C) a monomer having a photopolymerizable unsaturated bond in order to improve the photosensitive properties such as sensitivity and resolution. Further, it can be included.
  • the monomer having a photopolymerizable unsaturated bond is preferably a (meth) acrylic compound that can be radically polymerized by the above-mentioned (B) photopolymerization initiator.
  • polyethylene glycol diacrylate for each ethylene glycol unit 2 to 20
  • polyethylene glycol dimethacrylate number 2 to 20 of each ethylene glycol unit
  • poly (1,2-propylene glycol) diacrylate poly (1,2-propylene glycol) dimethacrylate
  • pentaerythritol diacrylate Pentaerythritol dimethacrylate
  • glycerol diacrylate glycerol dimethacrylate
  • dipentaerythritol hexaacrylate methylenebisacrylamide, N-methylolacrylamide
  • ethylene glycol jig Ricidyl ether-methacrylic acid adduct glycerol diglycidyl ether-acrylic acid adduct
  • bisphenol A diglycidyl ether-acrylic acid adduct bisphenol A diglycidyl ether-methacrylic acid adduct
  • the blending amount of the monomer (C) having a photopolymerizable unsaturated bond with respect to 100 parts by mass of the polyamide resin is preferably 1 to 40 parts by mass, and more preferably 1 to 20 parts by mass.
  • the photocrosslinking (photo radical polymerization) at the exposed part proceeds sufficiently during exposure, and a sufficiently good photosensitivity is ensured for practical use, and a relief pattern suitable for practical use. Can be obtained.
  • the blending amount is 40 parts by mass or less, it is possible to suppress unnecessary photocuring in the unexposed area due to light spots from the exposed area, that is, a post-development residue, and a relief pattern suitable for practical use. Can be obtained.
  • the residual monomer component which becomes a degassing component from the cured film can be suppressed even at low temperature curing, which is preferable.
  • the photosensitive resin composition of the present invention can further contain (D) a thermally crosslinkable compound in order to improve film properties (particularly heat resistance) after heat curing.
  • a thermally crosslinkable compound is (A) a compound that thermally crosslinks a polyamide resin, or a compound that itself forms a thermally crosslinked network.
  • a compound having an alkoxymethyl group as a thermally crosslinkable group for example, an amino resin or a derivative thereof is preferably used.
  • urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used. Particularly preferred is hexamethoxymethylated melamine.
  • the blending amount of the (D) thermally crosslinkable compound with respect to 100 parts by mass of the polyamide resin is preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass.
  • membrane characteristic after heat-hardening of the photosensitive resin composition of this invention can be improved further.
  • the said compounding quantity is 20 mass parts or less, the residual monomer component used as the degassing component from a cured film can be suppressed also in low temperature hardening.
  • the photosensitive resin composition of the present invention preferably contains (E) a silane coupling agent in order to improve photosensitive properties such as adhesion during development.
  • a silane coupling agent an organosilicon compound having a (dialkoxy) monoalkylsilyl group or a (trialkoxy) silyl group is preferable, for example, a compound represented by the following formula:
  • g is an integer of 1 or 2; when g is 1, Z is a divalent aromatic group; when g is 2, Z is a tetravalent aromatic group; A divalent organic group containing a carbon atom directly bonded to a silicon atom, d is an integer of 0 or 1, R 5 is a hydrogen atom or a monovalent hydrocarbon group, and R 6 and R 7 are respectively Independently, it is an alkyl group having 1 to 4 carbon atoms, and e is an integer of 0 or 1. ⁇ .
  • the silane coupling agent is obtained by reacting a (dialkoxy) monoalkylsilyl compound or (trialkoxy) silyl compound having an amino group with a dicarboxylic acid anhydride or a tetracarboxylic dianhydride and a derivative thereof. Can do.
  • dicarboxylic acid anhydride or tetracarboxylic dianhydride various structures can be used.
  • phthalic anhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride are particularly preferred in view of the effect of excellent adhesion to the base substrate and the price.
  • dialkoxy monoalkylsilyl compound and (trialkoxy) silyl compound having an amino group
  • various structures can be used, and examples thereof include the following (hereinafter, the notation of alkoxy is methoxy group or ethoxy).
  • 3-aminopropyltriethoxysilane is particularly suitable.
  • the silane coupling agent may be used alone or as a mixture of two or more.
  • the blending amount of the (E) silane coupling agent with respect to 100 parts by mass of the (A) polyamide resin is preferably 0.1 to 25 parts by mass, and more preferably 0.3 to 20 parts by mass.
  • the improvement effect of the adhesiveness of the photosensitive resin to a base substrate is favorable.
  • the said compounding quantity is 25 mass parts or less, the concern of precipitation by the dark reaction of the silane coupling agents in the photosensitive resin composition reduces significantly.
  • the photosensitive resin composition of the present invention improves adhesion of the photosensitive resin on a substrate (particularly a copper substrate) or suppresses discoloration of the copper substrate.
  • benzotriazole compounds include benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 4 (or 5) -carboxybenzotriazole, 4 (or 5)- Methylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -4 (or 5) -methylbenzotriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl] -4 (or 5) -Methylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-[(2-ethylhexylamino) methyl] -benzotriazole, 1- (1 ′, 2′-dicarboxyethyl) benzotriazole, N-benzotriazoyl Methylurea, 2,6-bis [(1H-benzotriazol-1-yl) me L] 4-methylphenol, 1- (2,3-dicarbox
  • 4 (or 5) -carboxybenzotriazole and 4 (or 5) -methylbenzotriazole are particularly preferable.
  • the benzotriazole-based compound may be a single compound or a mixture of two or more.
  • the blending amount of the (F) benzotriazole compound with respect to 100 parts by mass of the (A) polyamide resin is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass.
  • substrate (especially copper substrate) improves, and the effect which suppresses discoloration of a copper substrate expresses favorably.
  • the said compounding quantity is 10 mass parts or less, the fall of the adhesiveness of the photosensitive resin on a board
  • the photosensitive resin composition may contain a sensitizer for improving photosensitivity.
  • sensitizers include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino).
  • the sensitizer used may be a single or a mixture of two or more.
  • the blending amount of the sensitizer is preferably 0 to 15 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (A) polyamide resin.
  • the photosensitive resin composition of the present invention contains a polymerization inhibitor, if desired, for the purpose of improving the viscosity of the photosensitive resin composition solution during storage and the stability of photosensitivity. It can also be made.
  • polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid.
  • 2,6-di-tert-butyl-p-methylphenol 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N- Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw 4-hydroxy-3,5-di-tert- butyl) phenyl methane, or the like can be used.
  • the blending amount of the polymerization inhibitor is preferably 0 to 5 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (A) polyamide resin.
  • the photosensitivity suitable for practical use can be ensured favorably, without inhibiting the photocrosslinking reaction anticipated.
  • various additives such as a scattered light absorber and a coating film smoothness-imparting agent are added to the photosensitive resin composition according to need, as long as they do not inhibit the effects of the present invention. Can be appropriately blended.
  • the present invention also provides a photosensitive resin composition solution comprising the above-described photosensitive resin composition of the present invention and a solvent. It is preferable to use a photosensitive resin composition solution whose viscosity is adjusted by adding a solvent to the photosensitive resin composition.
  • Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone , ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, etc., and these may be used alone or in combination of two or more. Can be used. Among these, N-methyl-2-pyrrolidone and ⁇ -butyrolactone are particularly preferable.
  • solvents can be appropriately added to the photosensitive resin composition of the present invention depending on the coating film thickness and viscosity of the photosensitive resin composition solution. It is preferable to use in the range of 1,000 parts by mass.
  • alcohols shown below can be used in combination.
  • the alcohol is not particularly limited as long as it has an alcoholic hydroxyl group in the molecule, but specific examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol.
  • T-butyl alcohol benzyl alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, propylene glycol diethyl ether, propylene glycol mono (n-propyl) ether, propylene glycol di (n -Propyl) ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono (n-propyl) ether Ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, mono alcohols such as diethylene glycol monophenyl ether, ethylene glycol, and di alcohols such as propylene glycol.
  • benzyl alcohol and ethylene glycol monophenyl ether are particularly preferable.
  • the content ratio in the entire solvent is preferably 50% by mass or less.
  • the said ratio exceeds 50 mass%, there exists a tendency for the solubility with respect to this solvent of (A) polyamide resin to fall.
  • the present invention includes a step of applying the above-described photosensitive resin composition of the present invention or the photosensitive resin composition solution of the present invention on a substrate to form a coating film of the photosensitive resin composition, the coating film
  • a method for forming a cured relief pattern comprising a step of forming a relief pattern.
  • the example of the formation method of the hardening relief pattern of this invention is demonstrated below.
  • the photosensitive resin composition or the photosensitive resin composition solution of the present invention is applied on a base material such as a silicon wafer, an aluminum substrate, or a copper substrate.
  • a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used as the coating apparatus or coating method.
  • the coating film is dried by pre-baking at 80 to 120 ° C. to form a coating film of the photosensitive resin composition to a film thickness of about 5 to 50 microns.
  • the coating film formed above is irradiated with actinic rays directly or through a desired patterning mask (photomask) using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper. Exposure.
  • actinic rays X-rays, electron beams, ultraviolet rays, visible rays and the like can be used.
  • actinic rays having a wavelength of 200 to 500 nm are preferably used.
  • post-exposure baking or pre-development baking with any combination of temperature and time (preferably temperature 40 ° C. to 120 ° C., time 10 seconds to 240 seconds) is performed as necessary for the purpose of improving photosensitivity. You may give it.
  • the developing method can be selected from methods such as an immersion method, a paddle method, and a rotary spray method.
  • a good solvent for polyamide can be used alone, or a good solvent and a poor solvent for polyamide can be appropriately mixed and used.
  • Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, ⁇ -acetyl-gammabutyrolactone, cyclopenta Non, cyclohexanone and the like, and toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water and the like can be used as the poor solvent, respectively.
  • the mixing ratio is adjusted according to the solubility of the polyamide resin used, the developing method used, and the like.
  • an alkaline aqueous solution can also be used as a developer.
  • alkaline aqueous solutions include aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, aqueous solutions of organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, and tetrabutyl.
  • An aqueous solution of a quaternary ammonium salt such as ammonium hydroxide or the like, and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like, as necessary, can be used.
  • a relief pattern can be obtained by washing with a rinsing solution as necessary and removing the developer.
  • a rinsing solution distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used alone or in appropriate combination of two or more, and two or more can be used. It can also be used in combination in stages.
  • the relief pattern of the polyamide thus obtained is a cured relief pattern made of polyamide having excellent heat resistance and chemical resistance by appropriately heating, for example, to 150 to 350 ° C. to advance heat curing and crosslinking reaction. Is converted to Such a heat curing process can be performed using a hot plate, an inert oven, a temperature rising oven capable of setting a temperature program, or the like. Air may be used as the atmosphere for heat curing, and an inert gas such as nitrogen or argon may be used.
  • the present invention also provides a semiconductor device having a cured relief pattern formed by the above-described method for forming a cured relief pattern of the present invention.
  • the cured relief pattern produced as described above is used as a surface protection film, an interlayer insulation film, an ⁇ -ray shielding film, a partition, a dam, etc. of a semiconductor device built on a substrate such as a silicon wafer.
  • a semiconductor device can be manufactured by applying a known method for manufacturing a semiconductor device in the process. It is also possible to obtain a semiconductor device having a coating film made of a resin obtained by curing the above-described photosensitive resin composition of the present invention.
  • Table 1 shows a list of combinations of polymer raw materials of the following synthesis examples.
  • low molecular weight gel permeation chromatography ⁇ hereinafter referred to as low molecular weight GPC.
  • the reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate were acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of almost 100%.
  • reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand, and filtered after waiting for crystallization precipitation of the reaction product. After appropriately washing with water and vacuum drying at 40 ° C. for 48 hours, AIPA-BA in which the amino group of AIPA and the isocyanate group of 1,1-bis (acryloyloxymethyl) ethyl isocyanate acted was obtained.
  • the obtained AIPA-BA had a low molecular weight GPC purity of almost 100%.
  • AIPA-ME in which the amino group of AIPA and the isocyanate group of 2- (2-methacryloyloxyethoxy) ethyl isocyanate were reacted was obtained.
  • the obtained AIPA-ME had a low molecular weight GPC purity of almost 100%.
  • reaction solution was added to 15 liters of ion-exchanged water. The mixture was allowed to stand, stirred, and allowed to stand. After the crystallization and precipitation of the reaction product, the solution was filtered off, washed with water as appropriate, and dried in vacuo at 40 ° C.
  • AIPA-NBI amino group of AIPA and 5-norbornene-2,3 -AIPA-NBI having a norbornene imide structure was obtained by the action of an acid anhydride group of dicarboxylic acid anhydride.
  • the obtained AIPA-NBI had a low molecular weight GPC purity of almost 100%.
  • reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand, and filtered after waiting for crystallization precipitation of the reaction product. After appropriately washing with water and vacuum drying at 40 ° C. for 48 hours, AIPA-MA in which the amino group of AIPA and the acid chloride group of methacrylic acid chloride acted was obtained.
  • the obtained AIPA-MA had a low molecular weight GPC purity of almost 100%.
  • DCU dicyclohexylurea derived from a dehydrating condensing agent, which was precipitated in the polycondensation process ⁇ hereinafter referred to as DCU].
  • ⁇ was filtered under pressure, and while stirring the filtrate (polymer solution), a mixed solution of 840 g of water and 560 g of isopropanol was dropped, and the precipitated polymer was separated and redissolved in 650 g of NMP. This redissolved solution was added dropwise with stirring of 5 liters of ion-exchanged water to disperse and precipitate the polymer, recovered, washed with water, and then vacuum-dried at 40 ° C. for 48 hours to obtain polyamide PA-1.
  • the polystyrene-equivalent GPC weight average molecular weight (column: Shodex KD-806M ⁇ 2, NMP flow rate: 1.0 ml / min) measured using NMP as an eluent was 34,700.
  • a solution prepared by dissolving (0.28 mol) in 168 g of NMP was added dropwise over about 20 minutes, and the ice bath was removed for 3 hours while maintaining the temperature below 5 ° C. in an ice bath, followed by stirring at room temperature for 5 hours. Thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-3.
  • the polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 32,000.
  • the DCU precipitated in the polycondensation process is filtered off under pressure, and while stirring the filtrate (polymer solution), a mixed solution of 1,000 g of water and 4,000 g of isopropanol is added dropwise to separate the precipitated polymer. And redissolved in 800 g of NMP. This re-dissolved solution was dropped into 5 liters of ion-exchanged water with stirring to disperse and precipitate the polymer, recovered, washed with water, and then vacuum dried at 40 ° C. for 48 hours to obtain polyamide PA-6. .
  • the polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 32,600.
  • the DCU precipitated in the polycondensation process is filtered off under pressure, and while stirring the filtrate (polymer solution), a mixture of 760 g of water and 190 g of isopropanol is added dropwise to separate the precipitated polymer. Redissolved. This redissolved solution was dropped into 3 liters of ion-exchanged water with stirring to disperse and precipitate the polymer, recovered, washed with water, and then vacuum-dried at 40 ° C. for 48 hours to obtain polyamide PA-6. .
  • the polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 12,600.
  • the solution dissolved in was added dropwise over about 20 minutes, and the ice bath was removed for 3 hours while maintaining the temperature below 5 ° C., and then the ice bath was removed and the mixture was stirred at room temperature for 5 hours. Thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-12.
  • the polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 29,500.
  • Example 1 To 100 parts by mass of the polyamide PA-1 obtained in Synthesis Example 8, 190 parts by mass of NMP was added to dissolve the polyamide PA-1 to prepare a crude solution. This was a PTFE filter having a pore size of 0.2 microns. To obtain a resin solution V-1.
  • Example 2 The crude solution in Example 1 was filtered in the same manner as in Example 1 except that 5 parts by mass of 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime was further added as a photopolymerization initiator. A resin composition solution V-2 was obtained.
  • Example 3 Filtration was performed in the same manner as in Example 1 except that 8 parts by mass of tetraethylene glycol dimethacrylate as a photopolymerizable monomer was further added to the crude solution in Example 2 to obtain a resin composition solution V-3.
  • Example 4 Filtration was performed in the same manner as in Example 1 except that 5 parts by mass of hexamethoxymethylated melamine as a thermal crosslinking agent was further added to the crude solution in Example 3, to obtain a resin composition solution V-4.
  • Example 5 In the crude solution of Example 4, 5 parts by mass (1 part by mass as a pure component of S-1) of a 20% by mass NMP solution of the silane coupling agent S-1 obtained in Synthesis Example 6 was obtained. 10 parts by mass of a 20% by mass NMP solution of the silane coupling agent S-2 obtained in the above (2 parts by mass as a pure component of S-2), and 5 parts by mass of 3- (trialkoxysilyl) propylsuccinic anhydride A resin composition solution V-5 was obtained by filtration in the same manner as in Example 1 except for adding a part.
  • Example 6 Filtration was performed in the same manner as in Example 1 except that 2 parts by mass of 5-carboxybenzotriazole was further added to the crude solution in Example 5, to obtain a resin composition solution V-6.
  • Example 7 100 parts by mass of the polyamide PA-1 obtained in Synthesis Example 8 is 5 parts by mass of 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 8 parts by mass of tetraethylene glycol dimethacrylate, 5 parts by mass of hexamethoxymethylated melamine, 5 parts by mass of a 20% by mass NMP solution of the silane coupling agent S-1 obtained in Synthesis Example 6 ⁇ 1 part by mass as the pure content of S-1 ⁇ , Synthesis Example 7 10 parts by mass of a 20% by mass NMP solution of the silane coupling agent S-2 obtained in Step 2 (2 parts by mass as a pure component of S-2) and 5 parts by mass of 3- (trialkoxysilyl) propylsuccinic anhydride 2 parts by mass of 5-carboxybenzotriazole, 5 parts by mass of N, N-bis (2-hydroxyethyl) aniline, and 0.05 parts by mass of N-nitrosodipheny
  • Example 9 Polyamide PA-1 used in Example 7 was replaced with PA-3 obtained in Synthesis Example 10, and 3- (trialkoxysilyl) propyl succinic anhydride used in Example 7 was replaced with 3 -Resin composition solution V-9 was obtained in the same manner as in Example 7 except that it was replaced with isocyanatopropyltriethoxysilane.
  • Resin composition solution V- was prepared in the same manner as in Example 7, except that polyamide PA-1 used in Example 7 was replaced with polyamide PA-4 to PA-11 obtained in Synthesis Examples 11 to 18, respectively. 10 to V-17 were obtained.
  • Example 13 For the coating film of Example 13, 30 minutes after exposure, a 2.38% aqueous solution of tetramethylammonium hydroxide (product number AZ-300MIF, manufactured by AZ Electronic Materials) was used as a developer, and the unexposed area was completely Paddle development was performed by multiplying the time until dissolution disappeared by 1.4 by a time period, followed by rotary stream rinsing with ion-exchanged water to obtain a relief pattern made of a resin film.
  • tetramethylammonium hydroxide product number AZ-300MIF, manufactured by AZ Electronic Materials
  • the obtained relief pattern is visually observed under an optical microscope, and the minimum exposure (sensitivity) to obtain a sharp pattern without swelling, the dimension of the via hole (rectangular concave pattern) at the time of irradiation with the minimum exposure (resolution) Then, the adhesion to the substrate (pattern floating and peeling) was evaluated.
  • the results are shown in Table 2 below.
  • This resin film is cut to a width of 3.0 mm using a dicing saw (manufactured by Disco, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer, and a strip-shaped film sample It was.
  • This film sample was left in an atmosphere of 23 ° C. and 55% RH for 24 hours or more, and then a tensile test with Tensilon according to ASTM D-882-88 was performed to evaluate the elongation of the film sample. The results are shown in Table 2 below.
  • thermomechanical analyzer manufactured by Shimadzu Corporation, model name TMA-50
  • Tg glass transition temperature
  • the measurement conditions are a sample length of 10 mm, a constant load of 200 g / mm 2 , a measurement temperature range of 25 ° C. to 450 ° C., a temperature increase rate of 10 ° C./min, and a nitrogen atmosphere.
  • Table 2 The results are shown in Table 2 below.
  • This coating film was exposed with an i-line stepper exposure machine (manufactured by Nikon, model name NSR2005i8A) under conditions of a constant exposure amount through a photomask for evaluation.
  • the exposure amount was set by adding 200 mJ / cm 2 to each minimum exposure amount (sensitivity) at which a sharp pattern without swelling was obtained in the above-described evaluation of the photosensitive characteristics.
  • Example 13 For the coating film of Example 13, 30 minutes after exposure, a 2.38% aqueous solution of tetramethylammonium hydroxide (product number AZ-300MIF, manufactured by AZ Electronic Materials) was used as a developer, and the unexposed area was completely Paddle development was performed by multiplying the time until dissolution disappeared by 1.4 by a time period, followed by rotary stream rinsing with ion-exchanged water to obtain a relief pattern made of a resin film.
  • tetramethylammonium hydroxide product number AZ-300MIF, manufactured by AZ Electronic Materials
  • the coating film of Example 1 was not developed because the coating film had no photosensitivity.
  • the obtained relief pattern film (undeveloped flat film in Example 1) was heat-cured at 180 ° C. for 2 hours in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B).
  • the cured relief pattern film (cured flat film in Example 1) was produced.
  • This coating film was exposed with an i-line stepper exposure machine (manufactured by Nikon, model name NSR2005i8A) under conditions of a constant exposure amount through a photomask for evaluation.
  • the exposure amount was set by adding 200 mJ / cm 2 to each minimum exposure amount (sensitivity) at which a sharp pattern without swelling was obtained in the above-described evaluation of the photosensitive characteristics.
  • Example 13 For the coating film of Example 13, 30 minutes after exposure, a 2.38% aqueous solution of tetramethylammonium hydroxide (product number AZ-300MIF, manufactured by AZ Electronic Materials) was used as a developer, and the unexposed area was completely Paddle development was performed by multiplying the time until dissolution disappeared by 1.4 by a time period, followed by rotary stream rinsing with ion-exchanged water to obtain a relief pattern made of a resin film.
  • tetramethylammonium hydroxide product number AZ-300MIF, manufactured by AZ Electronic Materials
  • the relief pattern on the obtained copper substrate was heat-cured (cured) at 180 ° C. for 2 hours in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindbergh, model name VF-2000B) to obtain a copper A cured relief pattern on the substrate was prepared.
  • the copper substrate surface of the unexposed part was visually observed under an optical microscope, and the presence or absence of discoloration of the copper surface after curing was evaluated. The results are shown in Table 3 below.
  • Examples 1 to 17 excellent chemical resistance is achieved even at low temperature curing of 180 ° C. At the same time, high mechanical properties exhibiting an elongation of 50% or higher, excellent heat resistance exhibiting a Tg of 200 ° C. or higher, low residual stress characteristics of 25 MPa or lower, and a polyamide resin having unprecedented excellent low-temperature curing characteristics And the photosensitive resin composition containing this can be provided. Further, in Examples 3 to 17, excellent photosensitivity can be obtained, and in Examples 4 to 17, excellent heat resistance can be obtained. Further, in Examples 5 to 17, excellent adhesion during development can be obtained. Further, in Examples 6 to 17, discoloration of the copper surface after curing could be suppressed.
  • Comparative Example 1 is a case in which a polyamide resin made from a raw material made of a material in which a methacrylic group is directly linked to an amino group of AIPA and a radically polymerizable unsaturated bond group is introduced by a methacrylamide structure (AIPA-MA) is used.
  • AIPA-MA a methacrylamide structure
  • Comparative Examples 2 and 3 are cases where the copolymerization ratio of a radically unsaturated unsaturated group introduced into the amino group of AIPA (eg, AIPA-MO) is below the preferred range of the present invention.
  • the chemical resistance is also greatly inferior to that of the Examples, probably due to the decrease in the structure derived from AIPA, at the same time as the deterioration of the photosensitive characteristics due to the decrease in the radical polymerizable unsaturated bond group.
  • Comparative Example 4 is a case where a resin film made of a conventional photosensitive polyimide precursor composition is cured at a low temperature of 180 ° C., but imidization is incomplete, mechanical properties, heat resistance, residual stress, In any point of chemical resistance, it is remarkably inferior to the examples.
  • the photosensitive resin composition of the present invention and the polyamide resin used therefor are insulating materials for electronic components, surface protective films for semiconductor devices, interlayer insulating films, heat resistant coatings such as ⁇ -ray shielding films, and image sensors, It is suitable as a photosensitive resin composition used for forming a heat-resistant coating film in a semiconductor device or the like equipped with a micromachine or a microactuator.

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  • Physics & Mathematics (AREA)
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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Polyamides (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne une composition de résine photosensible ayant d'excellentes caractéristiques photosensibles, laquelle fournit un film de résine avec d'excellentes caractéristiques de film même lorsque le film de résine est formé dans des conditions de chauffage/durcissement telles qu'à 200 °C ou moins. L'invention concerne également une résine polyamide utilisée dans la composition de résine photosensible. La résine polyamide contient des unités structurales représentées par la formule (1) avec un nombre de répétition allant de 2 à 150, lequel est dans la plage allant de 80 à 100 % du nombre total d'unités structurales constituant la résine polyamide. [Dans la formule (1), X représente un groupe organique trivalent ayant de 6 à 15 atomes de carbone ; m représente 0 ou 2 ; Y représente un groupe organique divalent ayant de 6 à 35 atomes de carbone lorsque m représente 0, et représente un groupe organique tétravalent ayant de 6 à 35 atomes de carbone lorsque m représente 2 ; et R1 représente un groupe aliphatique ayant au moins un groupe de liaison insaturé polymérisable de manière radicalaire ayant de 5 à 20 atomes de carbone, lequel peut contenir un atome autre que les atomes de carbone.]
PCT/JP2009/060380 2008-06-09 2009-06-05 Résine polyamide, composition de résine photosensible, procédé de formation de motif en relief durci, et dispositif semi-conducteur Ceased WO2009151012A1 (fr)

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KR1020107006824A KR101187613B1 (ko) 2008-06-09 2009-06-05 폴리아미드 수지, 감광성 수지 조성물, 경화 릴리프 패턴의 형성 방법 및 반도체 장치
JP2010516837A JP5351155B2 (ja) 2008-06-09 2009-06-05 ポリアミド樹脂、感光性樹脂組成物、硬化レリーフパターンの形成方法及び半導体装置

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JP2011132533A (ja) * 2011-02-24 2011-07-07 Asahi Kasei E-Materials Corp アルカリ可溶性重合体、それを含む感光性樹脂組成物、及びその用途
CN102375336A (zh) * 2010-08-05 2012-03-14 旭化成电子材料株式会社 感光性树脂组合物、固化浮雕图案的制造方法及半导体装置
WO2012117786A1 (fr) * 2011-02-28 2012-09-07 富士フイルム株式会社 Composition photosensible, composition ainsi que film d'épargne de soudage photosensible, motif permanant ainsi que procédé de formation de celui-ci, et carte de circuit imprimé
WO2014003092A1 (fr) * 2012-06-29 2014-01-03 日産化学工業株式会社 Polyamide aromatique et composition filmogène le contenant
JP2018072456A (ja) * 2016-10-26 2018-05-10 東洋紡株式会社 凸版印刷原版用感光性樹脂組成物、及びそれから得られる凸版印刷原版
JP2018084626A (ja) * 2016-11-22 2018-05-31 日立化成デュポンマイクロシステムズ株式会社 感光性樹脂組成物、パターン硬化膜の製造方法、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品
CN109134845A (zh) * 2018-08-09 2019-01-04 东华大学 一种交联聚酰胺、增强纤维复合材料及其制备和应用
US10636845B2 (en) 2017-12-25 2020-04-28 Sakai Display Products Corporation Organic electroluminescent display apparatus
CN117420732A (zh) * 2023-12-19 2024-01-19 明士(北京)新材料开发有限公司 一种负型感光性树脂组合物及其应用

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JP6591058B2 (ja) * 2016-05-19 2019-10-16 三井化学株式会社 金属含有膜形成用組成物、金属含有膜形成用組成物の製造方法、半導体装置、及び半導体装置の製造方法
CN120802564A (zh) * 2018-10-03 2025-10-17 艾曲迪微系统股份有限公司 感光性树脂组合物、图案固化物的制造方法、固化物、层间绝缘膜、覆盖涂层、表面保护膜及电子部件
CN109814336B (zh) * 2019-01-21 2022-05-17 深圳市道尔顿电子材料有限公司 可碱溶负性光敏聚酰亚胺树脂组合物
CN110156985B (zh) * 2019-04-30 2021-12-21 珠海派锐尔新材料有限公司 一种高流动无规共聚半芳香尼龙及其制备方法
CN114690558A (zh) * 2022-03-17 2022-07-01 苏州理硕科技有限公司 一种聚酰胺类光刻胶组合物及其制备方法和应用

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Cited By (15)

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Publication number Priority date Publication date Assignee Title
CN102375336A (zh) * 2010-08-05 2012-03-14 旭化成电子材料株式会社 感光性树脂组合物、固化浮雕图案的制造方法及半导体装置
CN102375336B (zh) * 2010-08-05 2013-10-09 旭化成电子材料株式会社 感光性树脂组合物、固化浮雕图案的制造方法及半导体装置
JP2011132533A (ja) * 2011-02-24 2011-07-07 Asahi Kasei E-Materials Corp アルカリ可溶性重合体、それを含む感光性樹脂組成物、及びその用途
WO2012117786A1 (fr) * 2011-02-28 2012-09-07 富士フイルム株式会社 Composition photosensible, composition ainsi que film d'épargne de soudage photosensible, motif permanant ainsi que procédé de formation de celui-ci, et carte de circuit imprimé
US9382381B2 (en) 2012-06-29 2016-07-05 Nissan Chemical Industries, Ltd. Aromatic polyamide and film-forming composition containing same
JPWO2014003092A1 (ja) * 2012-06-29 2016-06-02 日産化学工業株式会社 芳香族ポリアミドおよびそれを含む膜形成用組成物
WO2014003092A1 (fr) * 2012-06-29 2014-01-03 日産化学工業株式会社 Polyamide aromatique et composition filmogène le contenant
JP2018072456A (ja) * 2016-10-26 2018-05-10 東洋紡株式会社 凸版印刷原版用感光性樹脂組成物、及びそれから得られる凸版印刷原版
JP2018084626A (ja) * 2016-11-22 2018-05-31 日立化成デュポンマイクロシステムズ株式会社 感光性樹脂組成物、パターン硬化膜の製造方法、硬化膜、層間絶縁膜、カバーコート層、表面保護膜及び電子部品
US10636845B2 (en) 2017-12-25 2020-04-28 Sakai Display Products Corporation Organic electroluminescent display apparatus
US11094747B2 (en) 2017-12-25 2021-08-17 Sakai Display Products Corporation Organic electroluminescent display apparatus
CN109134845A (zh) * 2018-08-09 2019-01-04 东华大学 一种交联聚酰胺、增强纤维复合材料及其制备和应用
CN109134845B (zh) * 2018-08-09 2021-01-05 东华大学 一种交联聚酰胺、增强纤维复合材料及其制备和应用
CN117420732A (zh) * 2023-12-19 2024-01-19 明士(北京)新材料开发有限公司 一种负型感光性树脂组合物及其应用
CN117420732B (zh) * 2023-12-19 2024-04-16 明士(北京)新材料开发有限公司 一种负型感光性树脂组合物及其应用

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