Classifications

• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • 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
  • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/84—Passivation; Containers; Encapsulations
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a production method of a polyhydroxyimide, particularly to a production method of a polyhydroxyimide aimed at improving problems in a thermal imidization method or a chemical imidization method, which is a production method of a polyimide in the related art.
• the present invention relates to a positive photosensitive resin composition containing the polyhydroxyimide obtained by the above production method, a cured film of the positive photosensitive resin composition, and various materials using the cured film.
• a method including: synthesizing a polyamic acid which is an imide precursor by reacting a tetracarboxylic dianhydride and a diamine as monomers; and imidizing the polyamic acid by using either (a) a thermal imidization method for cyclizing by heating and dehydrating or (b) a chemical imidization method for cyclizing using a dehydrocondensing agent and an imidization catalyst.
• the (a) thermal imidization method is a method for imidization in which a heating-dehydration reaction is effected by the use of an acid catalyst and an azeotropic solvent as assistants for the imidization reaction. At this time, generally, the polyamic acid is heated to a temperature of 180° C. to 250° C. to effect the reaction.
• the (b) chemical imidization method there is known a method in which a dehydrocondensing agent and a ring-closure catalyst are directly added to a polyamic acid solution to heat and dry the resultant mixture.
• a dehydrocondensing agent there are known carboxylic anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, and dicyclohexylcarbodiimide (DDC).
• aliphatic tertiary amines such as triethylamine
• heterocyclic tertiary amines such as isoquinoline, pyridine, ⁇ -picoline, aminopyridine and imidazole
• an acetic anhydride-pyridine type is widely used (for example, Patent Document 1).
• a polyimide resin is excellent in heat resistance, electric insulation, solvent resistance and mechanical stability, and is used in various fields.
• a cured film produced from a photosensitive polyhydroxyimide-based resin to which photosensitive properties are imparted by introducing a hydroxy group into a polyimide possesses not only the above characteristics of a polyimide-based resin, but also high resolution and high sensitivity. Therefore, the application of such a cured film has been expanded and starts to prevail not only in a semiconductor field, but also in a display field.
• Patent Document 2 a positive photosensitive resin composition using a polyhydroxyimide
• a polyhydroxyimide can be obtained from a precursor polyhydroxyamic acid by the (a) thermal imidization method or the (b) chemical imidization method.
• the (b) chemical imidization method even a hydroxy group in side chains of a polyamic acid is reacted with a large amount of acetic anhydride existing within the reaction system to be converted into an acetoxy group. This means that when a polyhydroxyimide is applied in a photosensitive resin composition or the like, a necessary developing group (hydroxy group) becomes deactivated.
• NMP N-methyl-2-pyrrolidone
• aromatic hydrocarbon solvent such as m-xylene
• a method for directly producing a polyhydroxyimide for example, by heating an acid dianhydride and a diamine at a high temperature (180° C.) in the presence of an acid catalyst ( ⁇ -valerolactone) and a base (pyridine) in a solvent mixture of an aprotic polar solvent (such as NMP) and a dehydrating solvent (such as toluene) to progress the reaction while azeotropically removing a water content (Patent Document 3).
• Patent Document 1 Japanese Patent Application Publication No. JP-A-2-151629
• Patent Document 2 Japanese Patent Application Publication No. JP-A-2005-173027
• Patent Document 3 Japanese Patent Application Publication No. JP-A-2002-212287
• a thermal imidization method requires such a high temperature as 180° C. and an azeotropic dehydration operation during the production, and a method for directly producing a polyhydroxyimide requires addition of a base and an azeotropic dehydrating solvent in comparison with a common production method of a polyimide.
• a thermal imidization method requires such a high temperature as 180° C. and an azeotropic dehydration operation during the production
• a method for directly producing a polyhydroxyimide requires addition of a base and an azeotropic dehydrating solvent in comparison with a common production method of a polyimide.
• a polyhydroxyamic acid obtained by reacting a component selected from a tetracarboxylic acid and a derivative of the tetracarboxylic acid with a diamine component having one or more hydroxy group(s), a polyhydroxyimide can be produced without requiring the use of a base or an azeotropic dehydration operation, and has completed the present invention.
• the present invention relates to, according to a first aspect, a production method of a polyhydroxyimide, characterized by including:
• X is a tetravalent aliphatic or aromatic group
• Y is an organic group containing an aromatic group substituted with at least one OH group
• n is an integer of 1 or more
• Y is an organic group containing a benzene ring substituted with at least one OH group.
• Y is an organic group containing two or more benzene rings substituted with at least one OH group.
• Y contains at least one type of structure selected from the structures of Formula (3) to Formula (5):
• R 1 to R 27 are independently a hydrogen atom, a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, a thienyl group which may be substituted with W or a furyl group which may be substituted with W, W is a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group, Z 1 to Z 6 are
• Z 1 to Z 6 are a single bond, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —C(O)NH—, —O—, —S(O) 2 — or —C(O)—.
• the carboxylic acid is a carboxylic acid of Formula (6):
• R 28 to R 30 are independently a hydrogen atom, a C 1-5 alkyl group, a C 1-5 haloalkyl group, a halogen atom, a nitro group, a phenyl group which may be substituted with W 2 , a naphthyl group which may be substituted with W 2 , a thienyl group which may be substituted with W 2 or a furyl group which may be substituted with W 2
• W 2 is a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group).
• the carboxylic acid of Formula (6) is a C 1-6 aliphatic carboxylic acid.
• R 28 to R 30 are a hydrogen atom or a halogen atom.
• the carboxylic acid of Formula (6) is acetic acid or trifluoroacetic acid.
• the acid component is added in a mass 0.1 to 2 times the mass of the polyhydroxyimide precursor of Formula (1).
• the heating temperature is 50 to 80° C.
• a production method of a polyhydroxyimide is characterized by including:
• A is either an organic group containing an aromatic group substituted with at least one OH group or a group of Formula (9):
• R 31 to R 34 are independently a hydrogen atom, a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group; a phenyl group which is optionally substituted with W 3 , a naphthyl group which is optionally substituted with W 3 , a thienyl group which is optionally substituted with W 3 or a furyl group which is optionally substituted with W 3 ,
• W 3 is a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group,
• Z 7 to Z 9 are independently a single bond, a C 1-10 alkylene group which is optionally substituted with W 4 , —C(O)O—, —C(O)NH—, —O—, —S—, —S(O) 2 — or —C(O)—, and W 4 is a C 1-10 alkyl group, a C 1-10 haloalkyl group or a C 1-10 alkoxy group)) (with proviso that the polyhydroxyimide precursor contains a unit structure containing the organic group containing an aromatic group substituted with at least one OH group and a unit structure containing the group of Formula (9)); and
• the organic group as A containing an aromatic group substituted with at least one OH group is an organic group containing a benzene ring substituted with at least one OH group.
• the organic group as A containing an aromatic group substituted with at least one OH group is an organic group containing two or more benzene rings substituted with at least one OH group.
• the organic group as A containing an aromatic group substituted with at least one OH group is an organic group containing at least one type of structure selected from structures of Formula (3) to Formula (5):
• R 1 to R 27 are independently a hydrogen atom, a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, a thienyl group which may be substituted with W or a furyl group which may be substituted with W, W is a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group, Z 1 to Z 6 are
• Z 1 to Z 6 are a single bond, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —C(O)NH—, —O—, —S(O) 2 — or —C(O)—.
• R 31 to R 34 are a methyl group
• Z 7 is —O—
• Z 8 and Z 9 are a propylene group.
• the carboxylic acid is a carboxylic acid of Formula (6):
• R 28 to R 39 are independently a hydrogen atom, a C 1-5 alkyl group, a C 1-5 haloalkyl group, a halogen atom, a nitro group, a phenyl group which may be substituted with W 2 , a naphthyl group which may be substituted with W 2 , a thienyl group which may be substituted with W 2 or a furyl group which may be substituted with W 2
• W 2 is a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group).
• the carboxylic acid of Formula (6) is a C 1-6 aliphatic carboxylic acid.
• R 28 to R 30 are a hydrogen atom or a halogen atom.
• the carboxylic acid of Formula (6) is acetic acid or trifluoroacetic acid.
• the acid component is added in a mass 0.1 to 2 times the mass of the polyhydroxyimide precursor having a unit structure of Formula (7).
• the heating temperature is 50 to 80° C.
• the imidization rate is 85% or more and a hydroxy group is not acetoxylated.
• a positive photosensitive resin composition contains the polyhydroxyimide as described in the twenty-fourth aspect as an (A) component and a compound generating an acid by being irradiated with light as a (B) component, both of which are dissolved in a (C) solvent.
• a positive photosensitive resin composition contains the polyhydroxyimide as described in the twenty-fifth aspect as an (A) component and a compound generating an acid by being irradiated with light as a (B) component, both of which are dissolved in a (C) solvent.
• the (B) component is a naphthoquinonediazide sulfonic acid ester compound.
• the (C) solvent is at least one type selected from a group consisting of an alcohol having 4 or more carbon atoms, and an alkyl ester.
• the positive photosensitive resin composition according to any one of the twenty-sixth aspect to the twenty-ninth aspect contains 0.01 to 100 parts by mass of the (B) component, based on 100 parts by mass of the (A) component.
• the positive photosensitive resin composition according to the thirtieth aspect further contains 5 to 100 parts by mass of a crosslinkable compound as a (D) component, based on 100 parts by mass of the (A) component.
• the present invention relates to a cured film obtained using the positive photosensitive resin composition as described in any one of the twenty-sixth aspect to the thirty-first aspect.
• the present invention relates to an electronic part having a cured film as described in the thirty-second aspect.
• the present invention relates to an organic EL element having a cured film as described in the thirty-second aspect.
• a forming method of a relief pattern includes: applying the positive photosensitive resin composition as described in any one of the twenty-sixth aspect to the thirty-first aspect on a substrate; heating and drying the composition; and irradiating the composition with an ultraviolet ray to develop a pattern.
• a polyhydroxyimide can be readily produced from a polyhydroxyamic acid without requiring a high temperature-heating operation, an azeotropic dehydration operation, addition of a base or an azeotropic dehydrating solvent, or the like, which are required during the production of a polyhydroxyimide in the related art.
• the reaction can be progressed at a reaction temperature of 100° C. or less, so that the production method of the present invention is an industrial production method having high practicality.
• the production method of the present invention can achieve the cost reduction or the like.
• the positive photosensitive composition of the present invention containing the polyhydroxyimide obtained by the above production method of the present invention does not cause such a large film loss of an unexposed portion as causing a problem during the development, and can form a fine pattern.
• a related-art production method of a polyhydroxyimide has problems that a side reaction is caused, that a synthetic method is cumbersome, and the like.
• a chemical imidization (using acetic anhydride and a base) method a hydroxy group is converted into an acetoxy group.
• a thermal imidization method requires a high temperature nearly 200° C. so that this method is unsuitable for the mass production, and the method also requires a process for an azeotropic operation or the like. Accordingly, these related-art production methods of a polyhydroxyimide are unsuitable as an industrial production method when a polyhydroxyimide is applied to a photosensitive resin composition.
• the present invention has such a characteristic that the present invention improves the problems of the related-art production method, for example, by using a weak acid such as acetic acid.
• the present invention relates to a production method of a polyhydroxyimide characterized by including adding an acid component that is at least one type of carboxylic acid having a pKa of 0 to 5 to a polyhydroxyimide precursor of Formula (1) or a polyhydroxyimide precursor having a unit structure of Formula (7), and heating the resultant mixture to a temperature of 50 to 100° C. to prepare a polyhydroxyimide having a weight average molecular weight of 3,000 to 100,000.
• the present invention relates to a positive photosensitive composition containing the polyhydroxyimide obtained by the above production method, a cured film of the positive photosensitive composition, and various materials using the cured film.
• the polyhydroxyimide precursor used in the present invention is produced containing a repeating unit of Formula (1):
• X is a tetravalent aliphatic or aromatic group
• Y is an organic group containing an aromatic group substituted with at least one OH group
• n is an integer of 1 or more.
• Y is preferably an organic group containing a benzene ring substituted with at least one OH group, particularly, Y is more preferably an organic group containing two or more benzene rings substituted with at least one OH group.
• Examples of Y include groups having structures of Formula (3) to Formula (5):
• R 1 to R 27 are independently a hydrogen atom, a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, a thienyl group which may be substituted with W or a furyl group which may be substituted with W;
• W is a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group;
• Z 1 to Z 6 are desirably a single bond, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —C(O)NH—, —O—, —S(O) 2 — or —C(O)—.
• Y is particularly preferably a group having an OH group at an o-position relative to a —NH group adjacent to Y among the groups of Formulae (3) to (5).
• polyhydroxyimide precursor used in the present invention contains a unit structure of Formula (7):
• X is a tetravalent aliphatic or aromatic group
• A is an organic group containing an aromatic group substituted with at least one OH group or a group of the following Formula (9).
• the above polyimide precursor contains both of a unit structure containing the organic group containing an aromatic group substituted with at least one OH group and a unit structure containing a group of the following Formula (9).
• R 31 to R 34 are independently a hydrogen atom, a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group, a sulfo group, a phenyl group which may be substituted with W 3 , a naphthyl group which may be substituted with W 3 , a thienyl group which may be substituted with W 3 or a furyl group which may be substituted with W 3 .
• W 3 is a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group, and Z 7 to Z 9 are independently a single bond, a C 1-10 alkylene group which may be substituted with W 3 , —C(O)O—, —C(O)NH—, —O—, —S—, —S(O) 2 — or —C(O)—.
• W 4 is a C 1-10 alkyl group, a C 1-10 haloalkyl group or a C 1-10 alkoxy group.
• examples of the organic group of A containing an aromatic group substituted with at least one OH group include the same as those defined as Y in Formula (1).
• R 31 to R 34 are a methyl group
• Z 7 is —O—
• Z 8 and Z 9 are a propylene group.
• a polyhydroxyimide precursor of Formula (1) (polyhydroxyamic acid) or a polyhydroxyimide precursor having a unit structure of Formula (7) (polyhydroxyamic acid) used in the present invention can be obtained, for example, by reacting a tetracarboxylic acid component with a diamine component.
• the tetracarboxylic acid component and the diamine component used in the present invention are not particularly limited. However, from the viewpoint of the solubility of the obtained polyhydroxyimide precursor in an organic solvent, it is preferred that at least one of the tetracarboxylic acid component and the diamine component contains a component having an organic group having fluorine at least in a part of the component.
• the organic group having fluorine in the tetracarboxylic acid component or the diamine component is not particularly limited. However, a fluoro group or a fluoroalkyl group directly bonded to a benzene ring is preferable.
• tetracarboxylic acid components or diamine components from the viewpoint of the solubility in a solvent, preferred are a tetracarboxylic acid component and a diamine component having a trifluoromethyl group or a hexafluoroisopropylidene group.
• a tetracarboxylic acid component and a diamine component having a trifluoromethyl group or a hexafluoroisopropylidene group preferred are preferred.
• one fluorine atom or a plurality of fluorine atoms may be bonded.
• the tetracarboxylic acid component that can be used as a monomer component constituting a polyhydroxyimide precursor of Formula (1) (polyhydroxyamic acid) or a polyhydroxyimide precursor of Formula (7) (polyhydroxyamic acid) that are used in the production method of the present invention is not particularly limited so long as the tetracarboxylic acid component is a tetracarboxylic acid, an acid dianhydride of the tetracarboxylic acid or a compound derived from the tetracarboxylic acid or the acid dianhydride of the tetracarboxylic acid. Specific examples of the tetracarboxylic acid component are described below.
• the specific examples include compounds such as aromatic tetracarboxylic acids such as pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 3,3′,4,4′-diphenylethertetracarboxylic acid, 3,3′,4,4′-diphenylsulfonetetracarboxylic acid, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, dianhydrides of these aromatic tetracarboxylic acids and derivatives of these aromatic tetracarboxylic acids or these dianhydrides; alicyclic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-tetramethyl-1
• examples of the tetracarboxylic acid component having an organic group having fluorine include compounds having a trifluoromethyl group or a hexafluoroisopropylidene group such as 2,2-bis(3,4-dicarboxyphenyl) hexafluoroisopropylidene, 4,4′-hexafluoroisopropylidenediphthalic acid, dianhydrides of these compounds and derivatives of these compounds or these dianhydrides, to which the examples are not limited.
• the tetracarboxylic acids and derivatives of the tetracarboxylic acids may be used individually or in combination of two or more types thereof.
• the diamine component as a monomer component constituting a polyhydroxyimide precursor (polyhydroxyamic acid) of Formula (1) used in the production method of the present invention is a diamine containing an aromatic group substituted with at least one OH group.
• the diamine component as a monomer component constituting a polyhydroxyimide precursor (polyhydroxyamic acid) having a unit structure of Formula (7) is a diamine containing an aromatic group substituted with at least one OH group and a diamine having a group of Formula (9).
• the diamine containing an aromatic group substituted with at least one OH group is not particularly limited and examples of such a diamine include 3,3′-diamino-4,4′-dihydroxybiphenyl (4BP), 3,3′-diamino-2,2′-dihydroxybiphenyl (2BP), 2,2′-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2,2-bis(4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane, bis(3-amino-4-hydroxyphenyl)methane (BAPF), 3,3′-diamino-4,4′-dihydroxybenzophenone (AHPK), 3,3′-diamino-4,4′-dihydroxy-phenyl ether (AHPE), 3,3′-di
• BAPF bis(3-amino-4-hydroxyphenyl)methane
• BAPA 2,2′-bis(3-amino-4-hydroxyphenyl) propane
• BAHF 2,2′-bis(3-amino-4-hydroxyphenyl) hexafluoropropane
• BAHF 3,3′-diamino-4,4′-dihydroxy-phenyl ether
• AHPK 3,3′-diamino-4,4′-dihydroxybenzophenone
• BSDA bis(3-amino-4-hydroxyphenyl) sulfide
• AHPA bis-amino-4-hydroxy)phenyl(3-amino-4-hydroxy) anilide
• BABHBPA bis-N,N′-(p-aminobenzoyl)-hexafluoro-2,2′-bis(4-hydroxyphenyl) propane
• the diamine having a group of Formula (9) is not particularly limited.
• preferred examples of the diamine include a siloxane-containing diamine.
• siloxane-containing diamines of Formula (10) As particularly preferred examples of the siloxane-containing diamine, siloxane-containing diamines of Formula (10):
• R 35 is a divalent organic group
• R 36 s are independently a monovalent organic group
• k is an integer of 1 or more
• APDS bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane
• diamine component that is a monomer component constituting a polyhydroxyimide precursor (polyhydroxyamic acid) used in the production method of the present invention
• diamine containing an aromatic group substituted with at least one OH group and the diamine having a group of Formula (9) other diamines can also be used.
• diamine components are not particularly limited. However, preferred is a diamine containing an aromatic group, and particularly desired is a diamine containing one or more benzene ring(s).
• diamine containing an aromatic group among the above other diamines examples include p-phenylene diamine, m-phenylene diamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4′-diaminodiphenyl ether (ODA), 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4-methylene-bis(2-methylaniline), 4,4′-methylene-bis(2,6-dimethylaniline), 4,4-methylene-bis(2,6-diethylaniline), 4,4′-methylene-bis(2-isopropy
• diamine examples include 4,4′-diaminodiphenyl ether (ODA) and 1,3-bis(4-aminophenoxy)benzene (DA4P).
• the polyhydroxyimide precursor (polyhydroxyamic acid) used in the production method of the present invention is obtained by subjecting the tetracarboxylic acid component and the diamine component (a diamine containing an aromatic group substituted with at least one OH group, or a diamine containing an aromatic group substituted with at least one OH group and a diamine containing a group of Formula (9)), and if desired, other diamine components to a polymerization reaction in an organic solvent.
• the organic solvent used for the polymerization reaction is not particularly limited so long as the organic solvent is a solvent capable of dissolving the generated polyhydroxyimide precursor.
• specific examples of the organic solvent include polar solvents such as N-methylpyrrolidone, dimethylacetamide, ⁇ -butyrolactone and diglyme. These solvents may be used individually or in combination of two or more types thereof. Further, even a solvent which cannot dissolve the polyhydroxyimide precursor may be mixed with the above organic solvent within a range in which the generated polyhydroxyimide precursor is not deposited.
• the lower limit of the temperature range for the reaction between the tetracarboxylic acid component and the diamine component is usually ⁇ 20° C. or more, preferably ⁇ 5° C. or more.
• the upper limit of the temperature range is usually 150° C. or less, preferably 100° C. or less, and from the range between the upper limit and the lower limit, an arbitrary temperature can be selected. It is desired that the reaction is effected preferably at room temperature.
• reaction temperature When the reaction temperature is set at a higher temperature, the polymerization reaction is rapidly progressed and is completed. However, when the reaction temperature is too high, a polyhydroxyimide precursor having a high molecular weight may not be obtained.
• the concentration of the solid content of both components (tetracarboxylic acid anhydride component and diamine component) in the solvent is not particularly limited.
• the concentration of the solid content is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• polyhydroxyimide precursor-containing solution can be used as it is, for the preparation of a polyhydroxyimide described below.
• the polyhydroxyimide precursor can be recovered to be used by precipitation-isolating the precursor in a poor solvent such as water, methanol and ethanol.
• the carboxylic acid having a pKa of 0 to 5 used in the present invention is preferably a carboxylic acid of Formula (6):
• R 28 to R 30 are independently a hydrogen atom, a C 1-5 alkyl group, a C 1-5 haloalkyl group, a halogen atom, a nitro group, a phenyl group which may be substituted with W 2 , a naphthyl group which may be substituted with W 2 , a thienyl group which may be substituted with W 2 or a furyl group which may be substituted with W 2 ; and W 2 is a C 1-10 alkyl group, a C 1-10 haloalkyl group, a C 1-10 alkoxy group, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group, a carboxyl group, a phospho group or a sulfo group.
• the carboxylic acid of Formula (6) is preferably a C 1-6 aliphatic carboxylic acid.
• Examples of such an aliphatic carboxylic acid include acetic acid, valeric acid, isovaleric acid, butyric acid, isobutyric acid, propionic acid, caproic acid, chloroacetic acid, dichloroacetic acid, bromoacetic acid, dibromoacetic acid, fluoroacetic acid, trifluoroacetic acid and pivalic acid.
• carboxylic acids a carboxylic acid in which R 28 to R 30 are a hydrogen atom or a halogen atom in Formula (6) is preferred; acetic acid and trifluoroacetic acid are more preferred in terms of easy availability; and acetic acid is most preferred from the viewpoint of safety.
• carboxylic acid used in the present invention is more preferably a carboxylic acid having a pKa of 3.8 to 5.
• an acid anhydride such as acetic anhydride used in a general production method of a polyimide as a dehydrocondensing agent doesn't correspond to the acid component (carboxylic acid) in the present invention.
• the acid component is added to the polyhydroxyimide precursor in a mass preferably 0.1 to 2 times, more preferably 0.1 to 1 time(s) the mass of the polyhydroxyimide precursor of Formula (1) or the polyhydroxyimide precursor having a unit structure of Formula (7).
• the production method of the polyhydroxyimide of the present invention is in detail a production method including: adding the acid component to the polyhydroxyimide precursor of Formula (1) or the polyhydroxyimide precursor having a unit structure of Formula (7) in an organic solvent; and heating the resultant mixture to a temperature of 50 to 100° C. to effect the reaction to produce a polyhydroxyimide.
• the organic solvent used in the production of the polyhydroxyimide precursor can be used.
• the polyhydroxyimide precursor solution obtained during the production of the polyhydroxyimide precursor as it is may be also used in the production of the polyhydroxyimide.
• the heating temperature is more preferably 50 to 80° C.
• the recovery of the thus obtained polyhydroxyimide is simply performed by a method including: charging the reaction mixture into a stirred poor solvent to precipitate the polyhydroxyimide; and filtering the precipitated polyhydroxyimide.
• the poor solvent used at this time is not particularly limited.
• examples of the poor solvent include methanol, hexane, heptane, ethanol, toluene and water.
• the recovered polyhydroxyimide can be converted into a polyhydroxyimide powder by drying the recovered polyhydroxyimide under normal pressure or reduced pressure either at normal temperature or by heating.
• the good solvent used at this time is not particularly limited so long as the solvent can dissolve the polyhydroxyimide.
• examples of the good solvent include N,N-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine and ⁇ -butyrolactone.
• the efficiency of the purification is furthermore enhanced.
• the positive photosensitive resin composition of the present invention is a composition containing: as the (A) component, the polyhydroxyimide of Formula (2) or the polyhydroxyimide having a unit structure of Formula (8) that are produced by the above production method; as the (B) component, a compound generating an acid by being irradiated with light; the (C) solvent in which the (A) component and the (B) component are dissolved; and if desired, a crosslinkable compound as the (D) component and other additives such as a surfactant.
• the (A) component is the polyhydroxyimide of Formula (2) or the polyhydroxyimide having a unit structure of Formula (8), each of which is produced by the above production method.
• n is desirably a positive integer of 1 to 1,000, particularly desirably a positive integer of less than 100.
• the type and the structure of the photoacid generator as the (B) component are not particularly limited so long as the photoacid generator has a function of enhancing the solubility of a light-irradiated portion of the resin composition in an alkaline developer by directly or indirectly generating an acid by being irradiated with light used for the exposure.
• the photoacid generators may be used individually or in combination of two or more types thereof.
• any one of the photoacid generators publicly known in the related art can be applied, and specific examples of the photoacid generator include o-quinonediazide compounds, allydiazonium salts, diallyliodonium salts, triallylsulfonium salts, o-nitrobenzyl esters, p-nitrobenzyl esters, trihalomethyl group-substituted s-triazine derivatives and imidesulfonate derivatives.
• a sensitizer can be used in combination with the photoacid generator as the (B) component.
• a sensitizer include perylene, anthracene, thioxanthone, Michler's ketone, benzophenone and fluorene, to which the examples are not limited.
• the o-quinonediazide compound is desired in terms of capability of obtaining high sensitivity and high resolution of a coating film obtained using the positive photosensitive resin composition.
• the o-quinonediazide compound is usually obtained as an o-quinonediazidesulfonic acid ester or an o-quinonediazidesulfonamide, by subjecting o-quinonediazidesulfonyl chloride and a compound having at least one group selected from a hydroxy group and an amino group to a condensation reaction in the presence of a basic catalyst.
• Examples of the o-quinonediazidesulfonic acid component constituting o-quinonediazidesulfonyl chloride include 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid and 1,2-naphthoquinone-2-diazide-6-sulfonic acid.
• the compound having a hydroxy group include: phenol compounds such as phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, o-methoxyphenol, 4,4-isopropylidene diphenol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidene diphenol, 4,4′,4′′-trihydroxytriphenylmethane, 1,1,1-tris(4-hydroxyphenyl)ethane, 4,4′-[1-[4[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, methyl 3,4,5-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, isoamyl 3,4,5-trihydroxybenzoic acid ester, 2-ethylbutyl 3,4,5-
• examples of the compound having an amino group include: anilines such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenylether; and aminocyclohexane.
• the compound having both a hydroxy group and an amino group include: aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4′-diamino-4′′-hydroxytriphenylmethane, 4-amino-4′,4′′-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, bis(4-amino-3-carboxy-5-hydroxyphenyl) sulfone, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl) propane and 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane; and alkanol amines such as 2-a
• o-quinonediazidesulfonyl chloride and a compound having at least any one group selected from a hydroxy group and an amino group to a condensation reaction, there is obtained a di-substituted, tri-substituted, tetra-substituted or penta-substituted o-quinonediazide compound in which a part of or the whole of hydroxy groups or amino groups of the compound is substituted with o-quinonediazidesulfonyl groups of o-quinonediazidesulfonyl chloride.
• the above multi-substituted o-quinonediazide compound is generally used individually or in combination of two or more types of multi-substituted compounds selected from the above multi-substituted compounds.
• o-quinonediazide compounds desired are o-quinonediazidesulfonic acid ester of p-cresol, o-quinonediazidesulfonic acid ester of 4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, o-quinonediazidesulfonic acid ester of methyl 3,4,5-trihydroxybenzoate, o-quinonediazidesulfonic acid ester of 2,3,4-trihydroxybenzophenone and o-quinonediazidesulfonic acid ester of 2,3,4,4′-tetrahydroxybenzophenone, and these compounds may be
• the content of the photoacid generator as the (B) component used in the present invention is 0.01 to 100 parts by mass, based on 100 parts by mass of the (A) component.
• the content of the photoacid generator as the (B) component is desirably 50 parts by mass or less, more desirably 30 parts by mass or less.
• the (C) solvent used in the positive photosensitive resin composition of the present invention in such terms that the solubility of the (A) component (a polyhydroxyimide of Formula (2) or a polyhydroxyimide having a unit structure of Formula (8)) in the solvent is high, that the compatibility of the solvent with the (B) component (photoacid generator) and with other components described below is advantageous, that the solvent is easily handled in the positive photosensitive resin composition, and that the solvent is a low-pollution organic solvent, an alkyl ester or an alcohol having 4 or more carbon atoms.
• a solvent examples include butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, ⁇ -butyrolactone, n-butanol, sec-butanol, tert-butanol, methoxymethylpentanol, methylcellosolve, ethylcellosolve, methylcellosolve acetate, ethylcellosolve acetate, butyl carbitol, butyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethy
• the positive photosensitive resin composition it is desired to use one type or a mixture of two or more types selected from a group consisting of butylcellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, methyl 2-hydroxyisobutyrate, ⁇ -butyrolactone and butyl lactate.
• the solvent is desirably selected from a group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, methyl 2-hydroxyisobutyrate and ⁇ -butyrolactone, and from the viewpoint of photosensitive property, the solvent is desirably selected from a group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 2-hydroxyisobutyrate and ⁇ -butyrolactone.
• solvents such as acetone, methanol, ethanol, isopropylalcohol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, ethylene glycol, ethylene glycol monoacetate, propylene glycol, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, N,N
• the positive photosensitive resin composition of the present invention may contain a crosslinkable compound as the (D) component.
• the crosslinkable compound as the (D) component is not particularly limited, so long as the crosslinkable compound is a compound having a group capable of being reacted with an organic group contained in the polyhydroxyimide as the (A) component in a process (hereinafter, called as “during the final curing”) for converting the coating film obtained using the positive photosensitive resin composition of the present invention into a cured film, and so long as the crosslinkable compound is a compound soluble in an alkaline developer in the developing process of the coating film obtained using the positive photosensitive resin composition.
• Examples of such a crosslinkable compound (D) include: maleimide compounds; compounds having two or more epoxy groups; and melamine derivatives, benzoguanamine derivatives and glycoluril that have a group in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group or both of them, however, in the present invention, the maleimide compound is preferably used.
• the structure of the maleimide compound is not particularly limited so long as a maleimide moiety is directly bonded to an aromatic ring and a hydrogen atom is directly bonded to an adjacent aromatic carbon.
• Examples of the maleimide compound having a structure in which a maleimide moiety is directly bonded to an aromatic ring and a hydrogen atom is directly bonded to an adjacent aromatic carbon include compounds of Formula (11).
• R 37 is a divalent group
• R 38 to R 47 are independently a hydrogen atom or a C 1-12 organic group.
• a maleimide compound having a structure in which in Formula (11), R 37 is a structure of Formula (12) is desirably used as the (D) component.
• h and i are independently 0 or 1
• R 48 to R 50 are independently a C 1-12 organic group or a divalent group having an oxygen atom, a sulfur atom or a nitrogen atom.
• maleimide compound of Formula (11) examples include compounds such as 2,2-bis(3-amino-4-maleimide) hexafluoropropane, 4,4′-dimaleimide diphenyl ether, 3,4′-dimaleimide diphenyl ether, 3,3′-dimaleimide diphenyl ether, 4,4′-dimaleimidediphenylsulfide, 4,4′-dimaleimidediphenylmethane, 3,4′-dimaleimidediphenylmethane, 3,3′-dimaleimidediphenylmethane, 4,4-methylene-bis(2-methylmaleimide), 4,4′-dimaleimidediphenylsulfone, 3,3′-dimaleimidediphenylsulfone, 1,4′-bis(4-maleimidephenoxy)benzene, 1,3′-bis(4-maleimidephenoxy)benzene, 1,3′-bis(4-maleimidephen
• 4,4′-dimaleimidediphenylmethane and 2,2′-bis[4-(4-maleimidephenoxy)phenyl]propane are preferred and further, from the viewpoint of photosensitivity property, 2,2′-bis[4-(4-maleimidephenoxy)phenyl]propane is more preferred.
• the maleimide compound used in the present invention as the (D) component may be used in combination of two or more types of maleimide compounds.
• the content of the crosslinkable compound as the (D) component in the positive photosensitive resin composition of the present invention is not particularly limited. However, it is desirably 5 to 100 parts by mass, more desirably 5 to 20 parts by mass, based on 100 parts by mass of the polyhydroxyimide as the (A) component.
• the positive photosensitive resin composition of the present invention may further contain surfactants, rheology controlling agents, adhesive assistants such as a silane coupling agent, pigments, dyes, preservation stabilizers, antifoamers or dissolution accelerators such as a polyphenol and a polycarboxylic acid.
• surfactants such as a silane coupling agent, pigments, dyes, preservation stabilizers, antifoamers or dissolution accelerators such as a polyphenol and a polycarboxylic acid.
• Examples of the surfactant capable of being used for the purpose of enhancing the coating property of the positive photosensitive resin composition of the present invention include fluorinated surfactants, silicon-based surfactants and nonionic surfactants.
• fluorinated surfactants for example, a commercialized product manufactured by Sumitomo 3M Limited, Dainippon Ink and Chemicals, Inc., Asahi Glass Co., Ltd., or the like can be used. These commercialized products are useful because of their easy availability.
• the commercialized surfactant include a fluorinated surfactant such as: EFTOP EF301, EF303, and EF352 (manufactured by JEMCO Inc.); MEGAFAC F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals Inc.); Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited); Asahi Guard AG 710, Surflon S-382, SC 101, SC 102, SC 103, SC 104, SC 105 and SC 106 (manufactured by Asahi Glass Co., Ltd.); and Ftergent series such as FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P and FTX-240G (manufactured by Neos Company Limited).
• surfactants may be used individually or in combination of two or more types thereof.
• the content of the surfactant in the positive photosensitive resin composition is usually 0.2% by mass or less, preferably 0.1% by mass or less, relative to 100% by mass of the positive photosensitive resin composition.
• the used amount of the surfactant is set at an amount of more than 0.2% by mass, the enhancing effect on the coating property is impaired, which is noneconomic.
• the positive photosensitive resin composition of the present invention is a composition that contains a polyhydroxyimide as the (A) component, a photoacid generator as the (B) component and the (C) solvent, and if desired, may further contain one or more type(s) of other additives such as a crosslinkable compound as the (D) component and a surfactant.
• positive photosensitive resin composition of the present invention include the following positive photosensitive resin compositions.
• (1) A positive photosensitive resin composition containing 100 parts by mass of the (A) component and 0.01 to 100 parts by mass of the (B) component, both of which are dissolved in the (C) solvent.
• the ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited so long as each component is homogeneously dissolved in a solvent. However, generally, by preparing a solution of a positive photosensitive resin composition having a concentration of the positive photosensitive resin composition optionally selected from a range of 1 to 50% by mass as the solid content concentration, the coating film of the composition can be easily formed.
• the solid content means a component remaining after subtracting the (C) solvent from the total component of the positive photosensitive resin composition.
• the preparing method of the positive photosensitive resin composition of the present invention is not particularly limited. This type of composition is usually used in a form of a solution, so that general examples of the preparing method of the positive photosensitive resin composition of the present invention include: a method by dissolving the (A) component, the (B) component and if desired, the (D) component in the (C) solvent to prepare a homogeneous solution; and a method by further blending other additives to the mixture of the components of the above preparing method at an appropriate step of the above preparing method.
• reaction solution obtained during the production of the (A) component that is, obtained by subjecting a component selected from a tetracarboxylic acid and a derivative of the tetracarboxylic acid, and a diamine component to a polymerization reaction in an organic solvent and to an imidization, as it is.
• examples of the organic solvent to be used at this time include the solvents described in the above examples of the (C) solvent.
• the (B) component when the (B) component is charged into the reaction solution of the (A) component in substantially the same manner as that in the above preparing method to prepare a homogeneous solution, for the purpose of controlling the concentration, the (C) solvent may be further charged, and at this time, an organic solvent used in the production of the (A) component and a (C) solvent used for controlling the concentration may be the same as or different from each other.
• the plurality of types of organic solvents may be mixed first, as well as optionally divided.
• the thus prepared solution of the positive photosensitive resin composition is preferably filtered using a filter having a pore diameter of around 0.2 ⁇ m to be used.
• a method including: applying the positive photosensitive resin composition of the present invention on an ITO substrate, a silicon wafer, a glass plate, a ceramics substrate or a substrate having an oxide film, a nitride film or the like by a publicly known method such as spin coating, immersion and printing; and predrying the composition at 60° C. to 160° C., desirably 70° C. to 130° C., a coating film produced from the positive photosensitive resin composition of the present invention can be formed.
• the coating film After the formation of the coating film, by exposing the coating film to, for example an ultraviolet ray using a mask having a predetermined pattern and by developing the coating film with an alkaline developer, an exposed portion is cleaning-removed and consequently, a relief pattern having a sharp edge face is formed on a substrate.
• the alkaline developer used here is not particularly limited so long as the alkaline developer is an alkaline aqueous solution and examples of the alkaline developer include: an aqueous solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate; an aqueous solution of a quaternary ammonium hydroxide such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and choline; and an aqueous solution of an amine such as ethanolamine, propylamine and ethylenediamine.
• an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate
• a quaternary ammonium hydroxide such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and choline
• an aqueous solution of an amine such as ethanolamine, propylamine and ethylene
• the concentration of the alkaline developer is generally 10% by mass or less, and industrially used is an alkaline aqueous solution having a concentration of 0.1 to 3.0% by mass.
• the alkaline developer may contain alcohols, surfactants or the like, each of which is desirably contained in a content of around 0.05 to 10% by mass.
• the temperature of the alkaline developer can be optionally selected.
• the solubility of an exposed portion is high, so that the development with an alkaline developer can be easily performed at room temperature.
• a substrate having the thus obtained relief pattern By subjecting a substrate having the thus obtained relief pattern to thermal treatment (baking) at a temperature of 180° C. to 400° C., it is possible to obtain a cured film with a relief pattern, which has low water-absorbency and consequently excellent electric property, advantageous heat resistance, and advantageous chemical resistance.
• the cured film obtained from the positive photosensitive resin composition of the present invention has such excellent effects, so that the cured film can be used for electric and electronic devices, semiconductor devices, display devices and the like.
• the cured film obtained from the positive photosensitive resin composition of the present invention has such a characteristic effect as having high reliability of the organic EL element (one type of light-emitting diode (LED) element), so that the cured film is extremely useful either as an insulating film and a diaphragm material for the organic EL element having a large problem of damage of a light emitting element, or for a buffer coating in which an ion migration of a copper wiring is largely influenced by the water absorbency of an insulating film in a semiconductor package.
• the organic EL element one type of light-emitting diode (LED) element
• Mw weight average molecular weight
• Mw molecular weight distribution
• the imidization rate was measured by measuring H-NMR (JNM-LA series; manufactured by JEOL Ltd.) and by calculating the imidization rate from a proton ratio of an aromatic moiety of a polymer skeleton, a proton ratio of an NH moiety of a polyamic acid and a proton ratio of a hydroxy group.
• the deuterated solvent dimethylsulfoxide was used as the deuterated solvent.
• the integration times were 64 times and the imidization rate was measured two times to calculate the imidization rate as an average value of two measured values.
• the imidization rate was 92% and a hydroxy group was confirmed.
• a polyhydroxyamic acid was synthesized using an acid dianhydride and an amine compound shown in Table 1 in substantially the same manner as that in Example 1.
• an acid component was added to the synthesized polyhydroxyamic acid and the resultant reaction mixture was heated at a temperature shown in Table 1 for 20 hours, followed by producing and recovering a polyhydroxyimide in substantially the same manner as that in Example 1.
• Comparative Example 1 in which the imidization was performed under a condition of a temperature (40° C.) lower than those in Examples, the polymer was hardly imidized.
• Comparative Example 2 using an imidization method of the related art using acetic anhydride and a basic solvent, though the imidization rate was high, hydroxy groups were acetoxylated.
• the positive photosensitive resin composition was applied on an ITO substrate (manufactured by Sanyo Vacuum Industries Co., Ltd.) having a step of 25 mm ⁇ 25 mm using a spin coater and was pre-baked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film.
• the film thickness was measured using a contact film thickness meter (trade name: Dektak 3ST; manufactured by ULVAC, Inc.)
• the obtained coating film was irradiated with ultraviolet light from an ultraviolet ray irradiating apparatus (trade name: PLA-501; manufactured by Canon Inc.) through masks having a line/space of 1, 2, 3, 4, 5, 6, 7, 8, 9, 20, 30, 40, 50, 70, 90 and 100 ⁇ M for 30 seconds (200 mJ/cm 2 ). After the exposure, the coating film was immersed in a tetramethylammonium hydroxide aqueous solution (2.38% by mass) of 23° C. for 30 seconds to develop a pattern and the film thickness after the development was measured.
• the coating film after the development was observed under an optical microscope and the minimum line width with which a line/space was formed without the peeling of the pattern was measured as the resolution.
• the cured films obtained from the positive photosensitive resin compositions of Examples 8 to 18 had a small film loss at an unexposed portion and on the cured films, a positive pattern with a resolution of 10 ⁇ m or less was obtained.
• the present invention is characterized by improving such problems in a production method of a polyhydroxyimide in the related art that a high-temperature heating process and a cumbersome production process are required.
• a polyhydroxyimide of the present invention by using a weak acid such as acetic acid, a polyhydroxyimide can be produced under a temperature condition of 10° C. or less without converting a hydroxy group into an acetoxy group, that is, without deactivating a developing group (a hydroxy group) necessary for, for example, utilizing the polyhydroxyimide as a photosensitive resin.
• a weak acid such as acetic acid
• the polyhydroxyimide obtained by the present invention is excellent in electric insulation, heat resistance, mechanical strength and electric properties which are the characteristics of an imide-based resin. Besides, the polyhydroxyimide obtained by the present invention enables production of a cured film excellent in sensitivity and resolution important for a photosensitive resin composition. In other words, the polyhydroxyimide can be applied to a production of a cured film capable of forming a high-resolution circuit pattern.
• the polyhydroxyimide of the present invention is suitable for a material for forming a cured film such as a protective film, a planarizing film and an insulating film in various displays such as a thin-film transistor liquid crystal display element and an organic EL element, particularly for a material for forming an interlayer insulating film for a TFT liquid crystal element, a color filter, an array planarizing film, a concavo-convex film as an underlayer of a reflecting film in a reflection-type display and an insulating film for an organic EL element.
• the production method of the present invention can produce a polyhydroxyimide from a polyhydroxyamic acid in one step and the simplification of the production process and the reduction of the cost can be expected to be achieved from the production method of the present invention in comparison with a related-art production method.
• the production method of the present invention can be utilized as an excellent industrial production method.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

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