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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • 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
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
• • 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
  • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • 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

Definitions

• the present invention relates to a photosensitive resin composition that is a precursor of a heat-resistant resin that can be used as a surface protective film and an interlayer insulating film of a semiconductor device, and a method for producing a cured relief pattern having heat resistance using the photosensitive resin composition And a semiconductor device having the cured relief pattern.
• Polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like are widely used for surface protective films and interlayer insulating films of semiconductor devices.
• This polyimide resin is currently generally provided in the form of a photosensitive polyimide precursor composition.
• the precursor composition is applied to a substrate such as a silicon wafer to form a precursor layer, the precursor layer is patterned using actinic rays, and the precursor layer is developed. Then, by subjecting the precursor layer to thermal imidization treatment, the polyimide resin film can be easily formed as a surface protective film, an interlayer insulating film or the like which is a part of the semiconductor device.
• the manufacturing process of a semiconductor device using a photosensitive polyimide precursor composition uses a conventional non-photosensitive polyimide precursor composition that needs to be patterned by a lithography method after forming a surface protective film or the like. Compared to the manufacturing process described above, the process can be greatly shortened.
• Patent Documents 1 and 2 disclose a method of using a precursor composition as a photosensitive resin composition, and has attracted attention in recent years.
• this photosensitive resin composition that is a PBO precursor composition is such that the naphthoquinone diazide compound (that is, the naphthoquinone diazide compound (ie This utilizes the fact that the photosensitive diazoquinone compound) is chemically changed to an indenecarboxylic acid compound and the dissolution rate of the exposed portion in the alkaline aqueous solution increases.
• the difference in dissolution rate with respect to the developer between the exposed portion and the unexposed portion a relief pattern composed of the unexposed portion can be produced.
• a positive relief pattern can be formed by exposing the PBO precursor composition described above and developing it with an alkaline aqueous solution. Further, when the PBO precursor composition is heated, an oxazole ring is formed, and the cured PBO film has the same thermosetting film characteristics as the polyimide film. Therefore, the PBO precursor composition is an organic solvent development type polyimide precursor. It has attracted attention as a promising alternative to body compositions.
• Patent Document 3 proposes a photosensitive resin composition comprising a phenolic hydroxyl group-containing solvent-soluble polyimide (hereinafter also referred to as “soluble PI”) and a naphthoquinonediazide compound.
• Patent Document 4 proposes a composition capable of negative patterning by adding a naphthoquinonediazide compound and a specific organic acid to a PBO precursor or PI precursor.
• Patent Document 5 proposes a highly sensitive photosensitive resin composition obtained by combining a PBO precursor with an organic acid such as m-toluic acid or m-anisic acid and an alcohol component as essential components.
• Patent Document 4 In the negative photosensitive system proposed in Patent Document 4, it is difficult to achieve high resolution, which is a positive characteristic. Further, in the technique of Patent Document 5, since the PBO precursor is volatilized at the time of forming the cyclized resin, further improvement in the remaining film ratio upon curing at the time of forming the cyclized resin has been demanded.
• the present invention relates to a photosensitive resin composition having a high-sensitive positive-type lithography performance with a high residual film ratio at the time of cyclized resin formation, and a method for producing a cured relief pattern using the photosensitive resin composition
• An object of the present invention is to provide a semiconductor device having the cured relief pattern.
• the present inventor solves the above problems by combining a photoacid generator and a specific monocarboxylic acid with a heat-resistant alkaline aqueous solution-soluble polymer having a specific structure, and cures when forming a cyclized resin.
• the present inventors have found that a photosensitive resin composition having a high positive-type lithographic performance with a high residual film rate can be obtained, and the present invention has been made. That is, the present invention is as follows.
• the (C) monocarboxylic acid compound is represented by the following general formula (3): (Wherein R 1 represents an organic group, R 2 represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group, and Z 1 represents a hydroxyl group, an ether group and an ester group) Represents a group having at least one functional group selected from the group consisting of groups.)
• the (C) monocarboxylic acid compound is represented by the following general formula (4): Wherein R 3 represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group, and R 4 represents at least a structure selected from the group consisting of a hydrogen atom, an alkyl group and a carbonyl group.
• Z 2 represents one group, Z 2 represents a hydroxyl group or an organic group, n 5 represents an integer of 0 to 5, and Z 2 may be the same or different from each other when a plurality of Z 2 are present.
• the photosensitive resin composition according to any one of the above [1] to [3], which is at least one compound selected from the group consisting of compounds represented by formula (8) and having 8 to 30 carbon atoms.
• the structure represented by the above general formula (1) in the (A) alkaline aqueous solution-soluble polymer has the following general formula (5):
• X 1 represents a divalent to tetravalent organic group having at least 2 carbon atoms
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• n 1 and n 3 is each independently an integer of 0 to 2
• m 1 is an integer of 1 to 1000
• L 1 , L 2 and L 3 are each independently Represents a hydrogen atom or a methyl group
• L 4 represents a hydrogen atom, a methyl group or a hydroxyl group.
• the structure represented by the above general formula (2) in the (A) aqueous alkali solution-soluble polymer is a structure represented by the following general formula (8) and a structure represented by the following general formula (9):
• X 4 represents a single bond and the following formula (7):
• the terminal of the above-mentioned (A) aqueous alkali-soluble polymer is represented by the following general formula (10):
• L 5 represents —CH 2 —, —O— or —S—
• L 6 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms.
• the compound (D) having three or more organic groups capable of crosslinking in the molecule is trimethylolpropane trimethacrylate, triallyl trimellitic acid, and the following general formula (11):
• D 1 is a group having at least one structure selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an organic group capable of crosslinking
• M 1 represents —CH 2 —, —O— or —S—
• Z 3 represents a divalent organic group
• n 6 represents an integer of 0 to 4
• D 1 represents , They may be the same or different when there are a plurality of them.
• the photosensitive resin composition as described in [9] above which is at least one compound selected from the group consisting of compounds represented by:
• the compound (D) having three or more organic groups capable of crosslinking in the molecule is represented by the following formula (12):
• a step of forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [11] on a substrate, (2) The photosensitive resin layer is exposed to actinic radiation through a mask to form an exposed portion, or an irradiated portion is formed by directly irradiating a part of the photosensitive resin layer with a light beam, an electron beam or an ion beam.
• the process of (3) A developing step of forming a relief pattern by eluting and removing the exposed portion or the irradiated portion of the photosensitive resin layer, and (4) forming a cured relief pattern by heat-treating the obtained relief pattern.
• the manufacturing method of a hardening relief pattern including the heating process to do.
• a photosensitive resin composition having a positive lithography performance that is highly sensitive and has a high residual film ratio at the time of curing when a cyclized resin is formed, and a cured relief pattern using the photosensitive resin composition And a semiconductor device having the cured relief pattern can be provided.
• the photosensitive resin composition according to the present invention is (A) The following general formula (1): (Wherein X 1 and Y 1 each independently represents a divalent to tetravalent organic group having at least two carbon atoms, and R 1 and R 2 each independently represents a hydrogen atom or the number of carbon atoms N 1 , n 2 , n 3 and n 4 each independently represents an integer from 0 to 2, n 1 + n 2 + n 3 + n 4 > 0, and m 1 1 is an integer from 1 to 1000.) And the following general formula (2): (Wherein X 2 and Y 2 each independently represents a tetravalent organic group having at least 2 carbon atoms, and m 2 is an integer of 1 to 1000) 100 parts by mass of an aqueous alkali solution-soluble polymer having at least one structure selected from the group consisting of the structures represented by (hereinafter also referred to as “(A) an aqueous alkali solution-soluble polymer”), (B)
• Alkaline aqueous solution-soluble polymer which is the base polymer of the photosensitive resin composition of the present invention, has the following general formula (1):
• X 1 and Y 1 each independently represents a divalent to tetravalent organic group having at least two carbon atoms
• R 1 and R 2 each independently represents a hydrogen atom or the number of carbon atoms N 1 , n 2 , n 3 and n 4 each independently represents an integer from 0 to 2, n 1 + n 2 + n 3 + n 4 > 0, and m 1 1 is an integer from 1 to 1000.
• X 2 and Y 2 each independently represents a tetravalent organic group having at least 2 carbon atoms, and m 2 is an integer of 1 to 1000
• It has at least 1 type of structure chosen from the group which consists of structure represented by these.
• Alkaline aqueous solution-soluble polymer is derived from an alkaline aqueous solution-soluble polymer which is a PBO precursor, an alkaline aqueous solution-soluble polyimide having a phenolic hydroxyl group, tetracarboxylic acid and diamine, and carboxylated at the ortho position of the amide bond. And a polyamic acid which is a polyimide precursor having a group, and a polyamic acid ester in which a part of the carboxyl group is sealed.
• the alkaline aqueous solution-soluble polymer may have a structure represented by the above general formula (1) and / or (2), but in order to control the alkali solubility of the resin, the above general formula (1) Or a repeating unit structure in which a part of the repeating unit structure represented by (2) is substituted.
• the aqueous alkali solution-soluble polymer has the following general formula (13) as a structure related to the general formula (1):
• X 1 and Y 1 each independently represents a divalent to tetravalent organic group having at least two carbon atoms
• R 1 and R 2 each independently represents a hydrogen atom or the number of carbon atoms 1 to 10 hydrocarbon groups
• n 1 , n 2 , n 3 and n 4 are each independently an integer of 0 to 2
• Y 3 each independently represents a divalent organic group having at least 2 carbon atoms
• m 1 is an integer of 1 to 1000
• m 3 is an integer of 1 to 500
• the arrangement order of m 1 units including X 1 and Y 1 and m 3 units including X 5 and Y 3 is not limited.
• the polymer having the structure represented by the general formula (13) includes a structure derived from X 1 (NH 2 ) 2 (OH) 2 (for example, bisaminophenol) and a structure of X 5 (NH 2 ) 2 . And a polymer having a structure derived from the diamine it has.
• the aqueous alkaline solution-soluble polymer has the following general formula (14) as a structure related to the general formula (2):
• X 2 , Y 2 and Y 4 each independently represents a tetravalent organic group having at least 2 carbon atoms
• X 6 is a divalent or 3 valent group having at least 2 carbon atoms.
• N 7 is 0 or 1
• m 2 is an integer of 1 to 1000
• m 4 is an integer of 1 to 500
• the order of arrangement of m 2 units and m 4 units including X 6 and Y 4 is not limited) You may have the structure represented by these.
• Examples of the polymer having the structure represented by the general formula (14) include a structure derived from X 2 (NH 2 ) 2 (OH) 2 (for example, bisaminophenol) and X 6 (NH 2 ) 2 (OH). And a polymer having a structure derived from a diamine having a structure of (for example, aminophenol) or X 6 (NH 2 ) 2 .
• X 1 is preferably a tetravalent organic group having 2 or more and 30 or less carbon atoms in view of good solubility in an alkali developer and heat resistance of the resulting resin film.
• Y 1 is preferably a divalent organic group having 2 to 30 carbon atoms in that the solubility in an alkali developer and the heat resistance of the resulting resin film are good.
• m 1 is an integer of 1 to 1000, more preferably an integer of 2 to 200, in view of good solubility in an alkali developer and mechanical properties of the resulting resin film. It is more preferably an integer, and most preferably an integer of 3 to 60.
• the m 3 diamide units in the general formula (13), which the aqueous alkali-soluble polymer has as necessary, are diamine having a structure of X 5 (NH 2 ) 2 and Y 3 (COOH) 2 . It has a structure obtained by polycondensation of a dicarboxylic acid having a structure.
• X 5 is preferably a divalent organic group having 2 to 30 carbon atoms in view of good solubility in an alkali developer and heat resistance of the resulting resin film.
• Y 3 is preferably a divalent organic group having 2 to 30 carbon atoms in view of good solubility in an alkali developer and heat resistance of the resulting resin film.
• m 3 is an integer of 1 to 500, and more preferably an integer of 1 to 10 in view of good solubility in an alkali developer and mechanical properties of the resulting resin film.
• the dihydroxydiamide unit has a structure obtained by polycondensation of a dicarboxylic acid having a Y 1 (COOH) 2 structure and a bisaminophenol having a X 1 (NH 2 ) 2 (OH) 2 structure.
• the two amino and hydroxy groups of the bisaminophenol are each in the ortho position.
• Dihydroxydiamide (hydroxypolyamide) is ring-closed by heating to about 250 to 400 ° C., and changes to polybenzoxazole which is a heat-resistant resin.
• Examples of the bisaminophenol having the structure of X 1 (NH 2 ) 2 (OH) 2 include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4 '-Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 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- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphen
• bisaminophenols having the structure of X 1 (NH 2 ) 2 (OH) 2
• X 1 is an aromatic group selected from the following.
• a compound having a structure of X 1 (NH 2 ) 2 (OH) 2 two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other (hereinafter referred to as “PBO precursor in the molecule”). It is also possible to use a "diamine having a structure”).
• the diamine represented by the following general formula obtained by reacting bisaminophenol having the structure of X 1 (NH 2 ) 2 (OH) 2 with two molecules of nitrobenzoic acid and reducing it may be mentioned. .
• X 7 represents a tetravalent organic group having at least 2 carbon atoms.
• X 7 is preferably at least one organic group selected from the group consisting of the organic groups described above as a preferred organic group represented by X 1 .
• the dicarboxylic acid dichloride having the structure of Y 5 (COCl) 2 is reacted with two molecules of nitroaminophenol for reduction. There are also ways to obtain the indicated diamines.
• Y 5 is a divalent organic group having at least 2 carbon atoms.
• Y 5 is preferably at least one organic group selected from the group consisting of organic groups described later as a preferred organic group represented by Y 1 .
• Examples of the diamine having the structure of X 5 (NH 2 ) 2 include aromatic diamine and silicon diamine.
• aromatic diamine examples include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino.
• Diphenyl ether 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2'-bis (4-aminophenyl) ) Propane, 2,2'-bis (4- Minophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benz
• a silicon diamine may be selected as part or all of the diamine having a structure of X 5 (NH 2) 2.
• silicon diamines include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis ( ⁇ -aminopropyl) tetramethyldi Examples thereof include siloxane, 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis ( ⁇ -aminopropyl) tetraphenyldisiloxane, and the like.
• Y 1 and Y 3 are respectively the following:
• a 1 is selected from the group consisting of —CH 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, and a single bond.
• L 8 , L 9 and L 10 each independently represent a hydrogen atom or a methyl group, and L 11 represents a hydrogen atom, a methyl group or a hydroxyl group.
• the structure represented by the above general formula (1) and the structure of the unit containing X 1 and Y 1 in the structure represented by the above general formula (13) are transparent in the i-line region and alkali in the exposed area.
• X 1 represents a divalent to tetravalent organic group having at least 2 carbon atoms
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• L 1 , L 2 and L 3 each independently represents a hydrogen atom or a methyl group
• L 4 represents a hydrogen atom, a methyl group or a hydroxyl group
• n 1 and n 3 each independently represents an integer of 0 to 2.
• m 1 is an integer from 1 to 1000.
• the structure represented by the above general formula (1) and the structure of the unit containing X 1 and Y 1 in the structure represented by the above general formula (13) are transparent in the i-line region and alkali in the exposed area.
• L 1 , L 2 and L 3 each independently represents a hydrogen atom or a methyl group
• L 4 represents a hydrogen atom or a methyl group. Or a hydroxyl group
• m 1 is an integer of 1 to 1000. It is preferable that the structure represented by these is included.
• Representative compounds as the dicarboxylic acid having a tricyclodecane skeleton, and a bis (carboxy) tricyclo [5,2,1,0 2,6] decane can be synthesized by a synthesis method according to Production Example A in JP-A No. 58-110538, a synthesis method according to Example 1 in JP-T-2002-504891, or a synthesis example in Synthesis Example 2 in JP-A No. 09-15846. Can be obtained according to the method. However, in these methods, since a heavy metal is used as an oxidizing agent, the following manufacturing method is more preferable in that no heavy metal is used. That is, tricyclo (5,2,1,0) decane dimethanol (catalog No.
• T0850 manufactured by Tokyo Chemical Industry Co., Ltd.
• Catalyst No. T0850 2,2,6,6-tetramethylpiperidine-1-oxyl
• Catalyst No. T0850 2,2,6,6-tetramethylpiperidine-1-oxyl
• TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
• the dicarboxylic acid compound which has a structure represented by the structure group of the said Formula (15) other than the compound mentioned above can be obtained with the following method, for example. That is, methylcyclopentadiene dimer (catalog No. M0920 manufactured by Tokyo Chemical Industry Co., Ltd.), 1-methyldicyclopentadiene (catalog No. M0910 manufactured by Tokyo Chemical Industry Co., Ltd.) or 1-hydroxydicyclopentadiene (catalog No. H0684 manufactured by Tokyo Chemical Industry Co., Ltd.) As a raw material. Org. Chem. , 45, 3527 (1980), hydrogen bromide or hydrogen chloride is added to the unsaturated bond site of the raw material. Am. Chem. Soc.
• derivatives of 5-aminoisophthalic acid can be used as part or all of the dicarboxylic acids having the Y 1 (COOH) 2 and Y 3 (COOH) 2 structures.
• Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydr
• a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with, for example, a monoalcohol or a monoamine can also be used.
• monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like
• monoamine include butylamine and aniline.
• examples of the above tetracarboxylic dianhydrides include the following chemical formula:
• a 2 is, -CH 2 -, - O - , - S -, - SO 2 -, - CO -, - NHCO- and -C (CF 3) 2 - 2 divalent selected from the group consisting of Represents a group of The compound represented by these is mentioned.
• tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.
• trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and the dicarboxylic acid obtained by ring opening in the same manner as the above tetracarboxylic dianhydride is used. It can also be used.
• the tetracarboxylic dianhydride obtained here has the following general formula:
• X 8 represents a divalent organic group represented by X 1 (OH) 2 (NH—) 2 , and X 1 has the same meaning as in general formula (1)). The compound represented by these is mentioned.
• dicarboxylic acid and bisaminophenol (diamine) for synthesizing dihydroxydiamide, which is a hydroxy polyamide, after obtaining diacid chloride using dicarboxylic acid and thionyl chloride
• examples thereof include a method in which bisaminophenol (diamine) is allowed to act on this, a method in which dicarboxylic acid and bisaminophenol (diamine) are polycondensed with dicyclohexylcarbodiimide, and the like.
• hydroxybenztriazole can be allowed to act simultaneously.
• the precursor having a repeating unit represented by the general formula (1) and the general formula (13) (for example, a PBO precursor) is sealed with an organic group (hereinafter also referred to as “sealing group”). It is also preferable to stop use.
• an organic group hereinafter also referred to as “sealing group”.
• a compound having an amino group or a hydroxyl group is used as a sealing group. Is preferred.
• Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate.
• the compound having a blocking group may be an acid anhydride, carboxylic acid, acid chloride, or isocyanate. It is preferable to use a compound having a group or the like.
• Examples of such compounds include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methyl cyclohexane dicarboxylic anhydride Products, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosyl chloride and the like.
• preferred end groups include the following general formula (10):
• L 5 represents —CH 2 —, —O— or —S—
• L 6 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms. To express.) The group represented by these is mentioned.
• (A) the aqueous alkali-soluble polymer has a structure represented by the general formula (2) or the general formula (14) will be described.
• a soluble PI structure is formed by the units containing X 2 and Y 2 in the general formulas (2) and (14).
• tetracarboxylic dianhydrides specifically Y 2 , or Y 2 and Y 4 are used.
• a tetracarboxylic dianhydride containing a tetravalent organic group is used.
• aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms and alicyclic tetracarboxylic dianhydrides having 6 to 34 carbon atoms are preferred in terms of solubility in solvents and aqueous alkali solutions. Compounds selected from those are preferred.
• the soluble PI structures represented by the general formula (2) and the general formula (14) are respectively represented by the following general formulas (1) from the viewpoint of the transparency of the i-line region and the solubility of the exposed portion in an alkaline developer. 8) and a structure represented by the following general formula (9):
• the dehydration condensation reaction when synthesizing an imide unit having a phenolic hydroxyl group is performed by, for example, following the method described in International Publication No. 01/034679 pamphlet with the above tetracarboxylic dianhydride and the above phenolic diamine as an acid catalyst. Alternatively, it can be carried out by heating to 30 ° C. to 220 ° C., preferably 170 ° C. to 200 ° C. in the presence of a base catalyst.
• the acid catalyst it is possible to use an inorganic acid such as sulfuric acid or an organic acid such as p-toluenesulfonic acid that is usually used in the production of polyimide. ⁇ -valerolactone and pyridine may be used.
• Examples of the base catalyst include pyridine, triethylamine, dimethylaminopyridine, 1,8-diazabicyclo (5,4,0) undecene-7, 1,3,5,7-tetraazatricyclo (3,3,1,1, 3,7) Decane, triethylenediamine or the like may be used.
• the temperature of the reaction solution is maintained at a temperature higher than the temperature at which the imidization reaction occurs, and water produced by the dehydration reaction is reacted with water using an azeotropic solvent such as toluene.
• the method may be used in which the imidization dehydration condensation reaction is completed.
• a polar organic solvent for dissolving an alkaline aqueous solution-soluble polymer soluble in an alkaline aqueous solution may be used as a reaction solvent in addition to toluene, which is a solvent for azeotropically distilling water.
• this polar solvent ⁇ -butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane and the like are used.
• the end of the soluble PI may be modified with, for example, the following compound.
• methods for modifying the terminal include maleic anhydride, succinic anhydride, cinnamic anhydride, 4-ethynylphthalic anhydride, phenylethynylphthalic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride , Cyclohexane-1,2-dicarboxylic acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, 4-aminostyrene, 4-ethynylaniline, 3-ethynylaniline, etc. The method of doing is mentioned. Moreover, you may leave dicarboxylic acid as a terminal.
• the terminal group of soluble PI is represented by the following general formula (10) from the viewpoint of sensitivity:
• L 5 represents —CH 2 —, —O— or —S—
• L 6 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms. Represents.
• the weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”) of the aqueous alkaline solution-soluble polymer is preferably 3,000 to 70,000, and preferably 6,000 to 50. Is more preferable.
• the weight average molecular weight is preferably 3,000 or more from the viewpoint of physical properties of the cured relief pattern. Moreover, from a viewpoint of resolution, 70,000 or less is preferable.
• As developing solvents for GPC tetrahydrofuran (hereinafter also referred to as “THF”) and N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) are recommended.
• THF tetrahydrofuran
• NMP N-methyl-2-pyrrolidone
• the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is recommended to be selected from Showa Denko
• the structure of both is obtained, for example, by cyclization condensation of tetracarboxylic dianhydride and an aromatic diamine having a phenolic hydroxyl group as a structure represented by the general formula (2) or (14).
• the polyimide skeleton having a phenolic hydroxyl group can be obtained by copolymerizing with the above-described polymerization component in the formation of the structure represented by the general formula (1) or (13).
• the copolymerization ratio at the time of copolymerization is arbitrarily selected, but the ratio of [structure represented by general formula (1) or (13)]: [structure represented by general formula (2) or (14)]
• the ratio of hydroxypolyamide: soluble PI is preferably in the range of 10:90 to 100: 0 from the viewpoint of photosensitivity.
• Photoacid generator As the photoacid generator, a compound having a naphthoquinonediazide structure, an onium salt, a halogen-containing compound and the like can be used. From the viewpoint of solvent solubility and storage stability, naphtho A compound having a quinonediazide structure (hereinafter also referred to as “naphthoquinonediazide compound”) is preferable.
• onium salt examples include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like, and onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts are preferable.
• halogen-containing compound examples include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable.
• the naphthoquinonediazide compound is typically a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure.
• the naphthoquinone diazide compound is typically a 1,2-naphthoquinone diazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinone diazide-5 of the polyhydroxy compound.
• -At least one compound selected from the group consisting of sulfonate esters hereinafter also referred to as "NQD compound").
• the NQD compound is obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride and subjecting the resulting naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound according to a conventional method.
• NQD compounds can be obtained by conducting esterification in the presence of a catalyst and washing the resulting product with water and drying.
• NQD compound those listed below are preferably used.
• each of R 15 and R 16 independently represents a hydrogen atom or at least one monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an allyl group, and a substituted allyl group.
• R 17 , R 18 , R 19 and R 20 each independently represents a hydrogen atom or an alkyl group, and m 5 is an integer of 1 to 5)
• R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or an alkyl group.
• the compound examples include NQD compounds of polyhydroxy compounds described in JP-A-2001-109149, (Chemical Formula 18) to (Chemical Formula 32).
• NQD compounds of the following polyhydroxy compounds are preferred because of their high sensitivity and low precipitation in the photosensitive resin composition.
• R 25 , R 26 , R 27, and R 28 each independently represent a monovalent organic group, and l is 0 or 1 M 6 , m 7 , m 8 and m 9 are each independently an integer of 0 to 3, and n 12 , n 13 , n 14 and n 15 are each independently an integer of 0 to 2. . ) An NQD compound of a polyhydroxy compound represented by the formula:
• Specific compounds include those described in (Chemical Formula 23) to (Chemical Formula 28) of JP-A No. 2001-092138.
• NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.
• L 12 and L 13 each independently represent a hydrogen atom or a monovalent organic group
• L 14 represents a monovalent organic group having one or more carbon atoms
• j represents 1 to An integer of 5 and m 10 is an integer of 3 to 8.
• NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.
• M 2 represents a divalent organic group containing an aliphatic tertiary or quaternary carbon
• a 3 represents the following chemical formula:
• Specific compounds include those described in (Chemical Formula 22) to (Chemical Formula 28) of JP-A No. 2003-131368.
• NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.
• L 15 represents —CH 2 —, —O— or —S—
• L 16 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms. Represents.
• L 17 represents —CH 2 —, —O— or —S—
• L 18 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms. Represents.
• R 29 , R 30 and R 31 are each independently represented by the following general formula:
• R 32 represents a hydrogen atom, or at least one monovalent organic group selected from an alkyl group and a cycloalkyl group, and m 14 is an integer of 0 to 2).
• m 11 , m 12 and m 13 are each independently an integer of 0 to 2.
• NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.
• R 33 represents a hydrogen atom or at least one monovalent organic group selected from the group consisting of an alkyl group, an alkoxy group, and a cycloalkyl group.
• NQD compounds of the following polyhydroxy compounds are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.
• R 34 represents the following general formula:
• R 38 represents a hydrogen atom or at least one monovalent organic group selected from the group consisting of an alkyl group and a cycloalkyl group, and m 18 is an integer of 0 to 2).
• R 35 , R 36 and R 37 are each independently at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group and a cycloalkyl group.
• m 15 , m 16 and m 17 are each independently an integer of 0 to 2.
• NQD compounds of polyhydroxy compounds described in (Chemical 15) and (Chemical 16) of JP-A-2005-008626 are preferable because of high sensitivity and low precipitation in the photosensitive resin composition.
• both a 5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazide sulfonyl group are preferable.
• the 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
• the 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
• a naphthoquinone diazide sulfonyl ester compound having both 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester. It can also be used as a mixture with a compound.
• the blending amount of the (B) photoacid generator is 1 to 50 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer, and 5 to 30 parts by mass. preferable.
• the compounding amount of the photoacid generator is 1 part by mass or more, the patterning property of the resin is good, and if it is 50 parts by mass or less, the tensile elongation of the cured film is good, and the exposure part There is little development residue (scum).
• the monocarboxylic acid compound is a monocarboxylic acid compound having at least one functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group at the ⁇ -position of the carboxyl group. It is a carboxylic acid compound.
• Examples of (C) monocarboxylic acid compounds include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy Examples include -2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, and ⁇ -methoxyphenylacetic acid.
• R 1 represents an organic group
• R 2 represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group
• Z 1 represents a hydroxyl group, an ether group and an ester group
• At least one compound selected from the group consisting of the compounds represented by formula (A) is preferred from the viewpoint of improving the residual film ratio upon curing.
• the compound represented by the general formula (3) preferably has 8 to 30 carbon atoms.
• Specific examples of the compound represented by the general formula (3) include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxy.
• Examples include mandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid and ⁇ -methoxyphenylacetic acid.
• R 3 represents a group having at least one structure selected from the group consisting of a hydrogen atom and an alkyl group
• R 4 represents at least a structure selected from the group consisting of a hydrogen atom, an alkyl group and a carbonyl group.
• Z 2 represents one group
• Z 2 represents a hydroxyl group or an organic group
• n 5 represents an integer of 0 to 5
• Z 2 may be the same or different from each other when a plurality of Z 2 are present.
• At least one compound selected from the group consisting of the compounds represented by formula (1) is more preferable from the viewpoint of further improving the residual film ratio upon curing.
• the compound represented by the general formula (4) preferably has 8 to 30 carbon atoms.
• Z 2 is an organic group
• Z 2 is preferably an organic group having 1 to 6 carbon atoms.
• Specific examples of the compound represented by the general formula (4) include 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, mandelic acid, atrolactic acid, O -Acetyl mandelic acid, ⁇ -methoxyphenylacetic acid and the like.
• R 4 is more preferably a group having at least one structure selected from the group consisting of an alkyl group and a carbonyl group as a substituent.
• Specific examples of such a compound include O-acetylmandelic acid and ⁇ -methoxyphenylacetic acid.
• the monocarboxylic acid compound has 8 or more carbon atoms from the viewpoint of improving the remaining film ratio upon curing.
• the number of carbon atoms is preferably 30 or less.
• the number of carbon atoms is more preferably 20 or less, and further preferably 15 or less.
• the monocarboxylic acid compound has a hydroxyl group, an ether group and an ⁇ group at the ⁇ -position of the carboxyl group. It has at least one functional group selected from the group consisting of ester groups.
• ether groups and ester groups are preferable from the viewpoint of good adhesion between the film and the substrate.
• the functional group sites are methylol groups, alkoxymethyl groups, etc. so that the carboxylic acid compound remaining after pre-baking does not volatilize the resin composition. Most preferably, it is a crosslinking group.
• Monocarboxylic acid compounds may be used alone or in admixture of two or more.
• the effect of adding a monocarboxylic acid compound is higher for the PBO precursor than for the soluble PI due to the difference in reactivity to the polymer.
• the blending amount of the above (C) monocarboxylic acid compound with respect to the aqueous alkali-soluble polymer is 5 to 20 parts by mass, preferably 5 to 10 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer.
• the compounding quantity of a carboxylic acid compound is 5 mass parts or more, the image development residue of an exposure part will decrease and the adhesiveness of the film
• the photosensitive resin composition of the present invention contains (D) a compound having three or more organic groups that can be crosslinked. It is preferable from the viewpoint of improving the residual film ratio and improving the glass transition temperature of the resin after the heat treatment. In particular, by combining the above-mentioned (C) monocarboxylic acid compound and (D) a compound having three or more organic groups capable of crosslinking, the thermal crosslinkability during curing of the photosensitive resin composition is improved.
• the compound having three or more organic groups capable of crosslinking is preferably a compound having 16 to 40 carbon atoms.
• the crosslinkable organic group possessed by the compound having three or more crosslinkable organic groups includes all organic groups known to those skilled in the art to have crosslinking reactivity. ) From the group consisting of acrylic, alkenyl, acetylene, thiol, disulfide, isocyanate, cyanate, methylol, alkoxymethyl, N-methylol, N-alkoxymethyl, silanol, and epoxy groups The at least 1 sort (s) of functional group chosen is mentioned.
• (meth) acryl group, alkenyl group, methylol group, alkoxymethyl group, N-methylol group and N-alkoxymethyl group are preferable, and the reactivity of the crosslinking group at low temperature is good.
• a (meth) acryl group and an alkenyl group are preferable.
• (D) Compounds having three or more organic groups capable of crosslinking include trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitic acid, pyromellitic acid tetraallyl ester, pentaerythritol pentaacrylate , Dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, and the following general formula (11):
• D 1 is a group having at least one structure selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an organic group capable of crosslinking
• M 1 represents —CH 2 —, —O— or —S—
• Z 3 represents a divalent organic group
• n 6 represents an integer of 0 to 4
• D 1 represents , They may be the same or different when there are a plurality of them.
• the compound represented by these is mentioned. Among them, from the viewpoint of sensitivity, trimethylolpropane trimethacrylate, trimaryl trimellitic acid, and a compound represented by the above general formula (11) are preferable.
• Specific examples of the compound represented by the general formula (11) include the following formula (12):
• BANI-X having a meta-xylylenediamine structure (manufactured by Maruzen Petrochemical Co., Ltd .: trade name) is most preferable from the viewpoint of the curing shape and sensitivity.
• a compound having three or more organic groups capable of crosslinking may be used alone or in combination of two or more.
• the blending amount in the case of containing a compound having three or more organic groups capable of crosslinking is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer.
• the amount is more preferably 30 parts by mass, and particularly preferably 4 to 20 parts by mass.
• hydroxyl group-containing compound a compound having 4 to 14 carbon atoms is preferable. Addition of a hydroxyl group-containing compound to the photosensitive resin composition of the present invention is preferable from the viewpoints of sensitivity and resolution.
• Specific examples of the hydroxyl group-containing compound include cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4-methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, and 4-ethylcyclohexanol.
• a monoalcohol is preferable to a diol. Is more preferable. Of these, 2,3,4-trimethyl-3-pentanol, 3-ethyl-2-methyl-3-pentanol, and glycerol- ⁇ , ⁇ '-diallyl ether are particularly preferable.
• hydroxyl group-containing compounds may be used alone or in combination of two or more.
• the amount of the hydroxyl group-containing compound to be blended is preferably 70 parts by weight or less, more preferably 0.01 to 70 parts by weight, and more preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the aqueous alkali solution-soluble polymer (A). 50 parts by mass is more preferable, 1 to 40 parts by mass is further preferable, and 5 to 25 parts by mass is particularly preferable.
• the compounding amount of the hydroxyl group-containing compound is 0.01 parts by mass or more, the development residue in the exposed area is reduced, and when it is 70 parts by mass or less, the tensile elongation of the cured film is good.
• phenol compound examples include ballast agents used in the above-mentioned naphthoquinonediazide compounds, and linear phenol compounds such as paracumylphenol, bisphenols, resorcinols, and MtrisPC and MtetraPC (trade names manufactured by Honshu Chemical Industry Co., Ltd.
• linear phenol compounds such as paracumylphenol, bisphenols, resorcinols, and MtrisPC and MtetraPC (trade names manufactured by Honshu Chemical Industry Co., Ltd.
• non-linear phenolic compounds such as TrisP-HAP, TrisP-PHBA, TrisP-PA (trade name) manufactured by Honshu Chemical Industry Co., Ltd., and 2-5 hydrogen atoms of the phenyl group of diphenylmethane were substituted with hydroxyl groups.
• a ballast agent means the phenol compound currently used as a raw material of the above-mentioned naphthoquinone diazide compound (photosensitive diazoquinone compound) which is a phenol compound by which a part of phenolic hydrogen atom was naphthoquinone diazide sulfonate esterified.
• the blending amount when blending the phenol compound is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer.
• the heat resistance of the film after thermosetting is good.
• the dye examples include methyl violet, crystal violet, and malachite green.
• the blending amount when the dye is blended is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer. When the blending amount is 0.1 parts by mass or more, the coloring effect is good, and when it is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.
• the surfactant examples include nonionic surfactants composed of polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether and derivatives thereof.
• Fluorado registered trademark
• MegaFac registered trademark
• Lumiflon registered trademark
• Fluorine-based surfactants such as
• organic siloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), and granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name) are listed.
• organic siloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), and granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name) are listed.
• the amount of the surfactant added is preferably 10 parts by mass or less, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer.
• the blending amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.
• adhesion aid examples include various silane coupling agents such as alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymer, and epoxy silane.
• silane coupling agent examples include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Silaace S810), 3-mercaptopropyltriethoxysilane.
• the blending amount in the case of blending the adhesion aid is preferably 20 parts by mass or less, more preferably 0.01 to 20 parts by mass or less, and more preferably 0.05 to 100 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer. 10 parts by mass is more preferable, 0.1 to 8 parts by mass is further preferable, and 1 to 6 parts by mass is particularly preferable.
• the adhesion assistant especially silicon-based coupling agent
• the adhesiveness is 20 parts by mass or less, the stability over time in the adhesiveness is good.
• the compounding amount of the above compound is preferably 0 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and particularly preferably 1 to 4 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer.
• the blending amount is 0.1 parts by mass or more, there is no development residue in the exposed part, the adhesion between the film formed using the photosensitive resin composition and the silicon substrate is good, and 10 parts by mass or less In this case, the stability over time in the adhesion is good.
• the photosensitive resin composition of the present invention is preferably dissolved in a solvent to form a varnish and used as a photosensitive resin composition solution.
• solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone (hereinafter also referred to as “GBL”), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide (hereinafter also referred to as “DMAc”).
• DMDG diethylene glycol dimethyl ether
• DMDG diethylene glycol diethyl ether
• diethylene glycol dibutyl ether propylene glycol monomethyl
• non-amide solvents are preferred because they have little influence on the photoresist and the like.
• Specific preferred examples include ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol and the like.
• These organic solvents may be used alone or in combination of two or more.
• the amount of the solvent added is preferably 100 to 2000 parts by mass, more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the (A) alkaline aqueous solution-soluble polymer. Viscosity can be controlled by changing the amount of the solvent added.
• the amount of the solvent added is preferably set so as to have a viscosity suitable for the coating apparatus and the coating thickness within the above range, from the viewpoint of easy production of the cured relief pattern.
• the present invention also provides a method for producing a cured relief pattern using the above-described photosensitive resin composition of the present invention.
• a step of forming a photosensitive resin layer comprising the above-described photosensitive resin composition of the present invention on a substrate (first step).
• the photosensitive resin composition is typically spin-coated using a spin coater or a die coater on a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate in the form of a photosensitive resin composition solution.
• a coater such as a roll coater.
• the substrate thus coated with the photosensitive resin composition solution is heated to 50 to 140 ° C., preferably 100 to 140 ° C. using an oven or a hot plate, and the solvent is removed by drying (hereinafter referred to as “soft baking”). Or a “pre-bake”), a photosensitive resin layer is formed on the substrate.
• the photosensitive resin layer is exposed to actinic radiation through a mask to form an exposed portion, or an irradiated portion is formed by directly irradiating a part of the photosensitive resin layer with a light beam, an electron beam or an ion beam.
• Step to perform (second step) the photosensitive resin layer is exposed with actinic radiation through a mask to form an exposed portion, or a light beam, an electron beam or an ion beam is directly irradiated to a part of the photosensitive resin layer to form an irradiated portion.
• actinic radiation is performed using a contact aligner or a stepper, or a predetermined portion of the photosensitive resin layer is directly irradiated with a light beam, an electron beam, or an ion beam.
• actinic rays which are actinic rays, for example, g-line, h-line, i-line and KrF laser can be used.
• a developing method methods such as spray, paddle, dip, and ultrasonic can be used.
• the rinsing liquid distilled water, deionized water, or the like can be used.
• the developer used for developing the photosensitive resin layer (A) dissolves and removes the aqueous alkali-soluble polymer and needs to be an alkaline aqueous solution in which an alkaline compound is dissolved.
• the alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.
• Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. , Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.
• organic alkali compound examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine.
• -N-propylamine isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.
• a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol
• a surfactant such as methanol, ethanol, propanol, or ethylene glycol
• a storage stabilizer such as a surfactant, a storage stabilizer, a resin dissolution inhibitor, and the like
• the obtained relief pattern is heat-treated (hereinafter, this process is referred to as “cure”).
• a heating device an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used.
• a heating method heating by hot air, infrared rays, electromagnetic induction, or the like is recommended.
• the heating temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C.
• the heating time is preferably 15 minutes to 8 hours, more preferably 1 hour to 4 hours.
• the atmosphere during heating is preferably in an inert gas such as nitrogen or argon.
• a cured relief pattern can be formed by the method as described above.
• the present invention also provides a semiconductor device having a cured relief pattern obtained by the manufacturing method of the present invention described above.
• the semiconductor device according to the present invention uses the above-described cured relief pattern as at least one of a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, and a protective film for a device having a bump structure. It can be manufactured by combining and forming a known method for manufacturing a semiconductor device.
• Teflon was attached (registered trademark) of anchor-type agitator, (manufactured by Tokyo Kasei Kogyo Co., Ltd.) to a glass separable three-necked flask, tricyclo [5,2,1,0 2,6] decanedimethanol 71.
• a solution obtained by diluting 143.2 g (1.267 mol) of 80% sodium chlorite with 850 mL of ion-exchanged water was added dropwise to the solution obtained above. Subsequently, 3.7 ml of 5% sodium dichlorite aqueous solution was diluted with 7 mL of ion-exchanged water and dropped into the solution. This solution was kept at 35 to 38 ° C. in a thermostatic bath and stirred for 20 hours to be reacted.
• reaction solution was cooled to 12 ° C., an aqueous solution in which 75 g of sodium sulfite was dissolved in 300 mL of ion-exchanged water was added dropwise to the reaction solution, and excess sodium chlorite was deactivated.
• the reaction solution was washed with ethyl acetate. Thereafter, 115 mL of 10% hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 3-4, and the precipitate was collected by decantation. This precipitate was dissolved in 200 mL of tetrahydrofuran.
• reaction solution was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm ⁇ 1 and 1772 cm ⁇ 1 appeared. .
• the weight average molecular weight (Mw) by the GPC (High Performance Liquid Chromatography) of the aqueous alkaline solution synthesized in this way is a single sharp curve of 14000 in terms of polystyrene, and a single composition is obtained. I confirmed that.
• the analysis conditions for GPC are described below.
• the weight average molecular weight by GPC of the aqueous alkali-soluble polymer synthesized in this way was a single sharp curve of 36800 in terms of polystyrene, and it was confirmed that a single composition was obtained.
• the analysis conditions for GPC are described below.
• the reaction solution obtained above was dropped into 3 liters of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water and dehydrated, and then vacuum dried to obtain an aqueous alkali-soluble polymer (P-3). Soluble PI was obtained.
• the weight average molecular weight by GPC of the aqueous alkali-soluble polymer synthesized in this manner was a single sharp curve of 23000 in terms of polystyrene.
• the analysis conditions for GPC are described below.
• the suspension was similarly added over 60 minutes with stirring under ice cooling. After stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour. After further adding 250 ml of DMAc and 400 ml of THF, the precipitate was removed by suction filtration, and the resulting reaction solution was added to 15 l of ethyl alcohol.
• the resulting precipitate was filtered off and dried under vacuum to obtain a PI precursor as polyamic acid ester (P-4).
• the weight average molecular weight by GPC of the aqueous alkaline solution polymer synthesized in this manner was a single sharp curve of 33000 in terms of polystyrene.
• the analysis conditions for GPC are described below.
• the product is imidized, it is not characteristic absorption of amide groups in the vicinity of 1540 cm -1 and 1650 cm -1 appear characteristic absorption of an imide group 1394Cm -1 and 1774 cm -1 in the IR spectrum are present, as well as NMR spectrum This was confirmed by the absence of proton peaks of amide and carboxylic acid.
• C-1) 3-phenyllactic acid (C-2) hydroxymandelic acid (C-3) 4-hydroxy-3-methoxymandelic acid (C-4) mandelic acid (C-5) atrolactic acid (C-6) ) O-acetylmandelic acid (C-7) ⁇ -methoxyphenylacetic acid (C-8) 2-phenylbutyric acid (C-9) 3- (4-hydroxyphenyl) propionic acid (C-10) tropic acid (C— 11) m-Toluic acid (D-1) BANI-X (Maruzen Petrochemical: trade name) (D-2) Trimethylolpropane trimethacrylate (D-3) Triaryl trimellitic acid
• Sensitivity (mJ / cm 2 ) was defined as the minimum exposure amount that could completely dissolve and remove the exposed portion of the coating film at the specified post-development film thickness. [Remaining film rate during curing (%)] The residual film ratio (%) upon curing was defined as (film thickness of cured relief pattern after curing) / (film thickness of relief pattern after development) ⁇ 100.
• the photosensitive resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, It can be suitably used as a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

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