WO2009145065A1 - 新規なポリイミド前駆体組成物、その利用及びそれらの製造方法 - Google Patents
新規なポリイミド前駆体組成物、その利用及びそれらの製造方法 Download PDFInfo
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- WO2009145065A1 WO2009145065A1 PCT/JP2009/058974 JP2009058974W WO2009145065A1 WO 2009145065 A1 WO2009145065 A1 WO 2009145065A1 JP 2009058974 W JP2009058974 W JP 2009058974W WO 2009145065 A1 WO2009145065 A1 WO 2009145065A1
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- Prior art keywords
- polyimide precursor
- precursor composition
- general formula
- solution
- bis
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- 0 [O-][N+](*12[N+]([O-])O[N+]1[O-])O[N+]2[O-] Chemical compound [O-][N+](*12[N+]([O-])O[N+]1[O-])O[N+]2[O-] 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- PYNJFYOXOOQZFM-UHFFFAOYSA-N [O-][NH+]([N]12[NH+]([O-])O[NH+]1[O-])O[NH+]2[O-] Chemical compound [O-][NH+]([N]12[NH+]([O-])O[NH+]1[O-])O[NH+]2[O-] PYNJFYOXOOQZFM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/346—Polycarboxylic acids having at least three carboxylic acid groups having four carboxylic acid groups
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- 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
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- 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
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- 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
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Definitions
- the present invention relates to a polyimide precursor composition that can be cured at a low temperature of 250 ° C. or less and has excellent long-term storage stability, a method for producing the same, and a polyimide precursor solution, a polyimide coating film, and a photosensitive resin obtained from the polyimide precursor composition.
- the present invention relates to a composition and a method for producing the composition.
- Polyimide resin is used for electrical and electronic applications because of its excellent heat resistance, electrical insulation and chemical resistance, and excellent mechanical properties. For example, it is used to form insulating films and protective coatings on semiconductor devices, surface protective materials such as flexible circuit boards and integrated circuits, base resin, and fine circuit interlayer insulating films and protective films. .
- a protective material obtained by bonding a molded body such as a polyimide film with an adhesive or a liquid polyimide resin solution has been used.
- polyimide resin solutions There are roughly two types of polyimide resin solutions.
- One type is a polyamic acid solution that is a precursor of a polyimide resin
- the other type is a solution of a polyimide resin that is soluble in an organic solvent.
- these polyamic acid solutions and polyimide solutions are high molecular weight polymer solutions, the molecular weight is large and the solubility is low, so the concentration of the solute cannot be adjusted to a high concentration.
- the salt solution using tetracarboxylic acid or its diester acid derivative and diamine described in Patent Documents 1 to 4 has a very high imidization temperature and does not become a solution of a salt that can be cured at low temperature. Became clear.
- the polyamic acid solution having an amide bond described in Patent Documents 5 to 7 the amide bond is broken and the solution stability is poor. Particularly, when the solution is prepared at a high concentration, the amount of change in the solution viscosity is large. It became clear that there is.
- an object of the present invention is to provide a polyimide precursor solution that can be cured at a low temperature (250 ° C. or lower) and has a low viscosity despite its high concentration, a method for producing the same, and good physical properties obtained therefrom. It is in providing the polyimide coating film which has, and the photosensitive resin composition and its manufacturing method.
- the present inventors have found that a polyimide coating film having good physical properties can be obtained by low-temperature curing from a composition containing an imidized tetracarboxylic acid and an isocyanate compound. I found it. That is, the polyimide precursor composition containing an imidized tetracarboxylic acid and an isocyanate-based compound represented by the general formula (1) described later has a high concentration of solute dissolved in a solution.
- the inventors have obtained knowledge that a low-strength and high-strength polyimide coating film can be obtained from this solution, and the present invention has been achieved based on these findings.
- the present invention can solve the above problems with a polyimide resin precursor composition having the following novel configuration.
- each R independently represents a tetravalent organic group
- each R ′ independently represents a divalent organic group
- l represents an integer of 0 to 20.
- It is a polyimide precursor composition characterized by including the imidized tetracarboxylic acid shown in (5), and an isocyanate type compound.
- polyimide precursor composition is further represented by the following general formula (2)
- R ′′ represents a divalent organic group. It is preferable that it is a polyimide precursor composition characterized by including the diamine shown in.
- R represents the following general formula group (1)
- R ′ in the general formula (1) represents the following general formula group (2)
- R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group.
- M represents an integer of 1 to 40, and n represents an integer of 1 to 20.
- R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms. It preferably contains at least a divalent organic group represented by
- R ′′ in the general formula (2) represents the following general formula group (3)
- R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group.
- M represents an integer of 1 to 40, and n represents an integer of 1 to 20.
- R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms. It is preferably a divalent organic group selected more.
- Still another invention of the present invention is a polyimide precursor composition solution obtained by dissolving a polyimide precursor composition to a solute concentration of 40 to 90% by weight.
- another invention of the present invention is a polyimide coating film obtained from the polyimide precursor composition or the polyimide precursor composition solution.
- another invention of the present invention is a printed wiring board with a polyimide coating obtained by applying the polyimide precursor composition or the polyimide precursor composition solution to a printed wiring board and imidizing by heating.
- another invention of the present invention is a photosensitive resin composition
- a photosensitive resin composition comprising the polyimide precursor composition, at least a photosensitive resin, and a photopolymerization initiator.
- R represents a tetravalent organic group.
- R ′ represents a divalent organic group.
- the diamine represented by the general formula (4) is represented by the following general formula group (4).
- R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group.
- M represents an integer of 1 to 40, and n represents an integer of 1 to 20.
- R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms. It is preferable that at least the diamine shown by these is included.
- Another invention of the present invention includes a step of dissolving a polyimide precursor composition obtained by the above production method in an organic solvent so as to have a solute concentration of 40 to 90% by weight. It is a manufacturing method of a physical solution.
- another invention of the present invention is a method for producing a polyimide coating film, comprising the step of obtaining a polyimide coating film from the polyimide precursor composition obtained by the production method or the polyimide precursor composition solution. is there.
- another invention of the present invention includes a step of applying a polyimide precursor composition obtained by the above production method or the polyimide precursor composition solution to a printed wiring board and heating to imidize. It is a manufacturing method of the printed wiring board with a polyimide coating film.
- another invention of the present invention is a photosensitive resin composition characterized by comprising a step of mixing at least a photosensitive resin and a photopolymerization initiator with a polyimide precursor composition obtained by the above production method. It is a manufacturing method.
- the polyimide precursor composition of the present invention When the polyimide precursor composition of the present invention is dissolved in an organic solvent, the solution has a low viscosity even though the solute is dissolved at a high concentration. And the polyimide coating film obtained from the polyimide precursor composition of this invention is excellent in the adhesiveness of a coating film, environmental test stability, chemical resistance, and flexibility, and has a favorable physical property. Therefore, the polyimide precursor composition of the present invention can be used as a protective film for various wiring boards, and has excellent effects. In addition, the photosensitive resin composition using the polyimide precursor composition of the present invention can be cured at a low temperature, and exhibits a variety of excellent properties when applied and molded on a wiring board. It is a thing.
- a polyimide precursor solution that dissolves at a high concentration and has a low viscosity can be easily produced.
- a polyimide coating film can be easily produced.
- a photosensitive resin composition having various excellent properties can be produced as a photosensitive resin composition.
- the polyimide precursor composition of the present invention has at least the following general formula (1)
- each R independently represents a tetravalent organic group
- each R ′ independently represents a divalent organic group
- l represents an integer of 0 to 20.
- the polyimide precursor composition of the present invention contains the structure of the above general formula (1) and an isocyanate compound, but each does not have a covalent bond. That is, the general polyimide precursor composition indicates, for example, a polymer in which the general formula (1) and the aromatic diamine are partially covalently bonded by an amide bond, but the polyimide precursor composition of the present invention has the general formula.
- the imidized tetracarboxylic acid is represented by the following general formula (1)
- each R independently represents a tetravalent organic group
- each R ′ independently represents a divalent organic group
- l represents an integer of 0 to 20.
- the imidized tetracarboxylic acid of the present invention is preferably as the molecular weight is short because the solubility in an organic solvent solution is improved.
- a polymer called an oligomer having a relatively low molecular weight is preferable.
- the solubility to a solvent can be improved.
- the bond in the structure is not an amide bond but an imide bond, the storage stability is excellent. Therefore, when the polyimide precursor composition solution is prepared, deterioration of the solution viscosity with time can be prevented, and a change in viscosity can be suppressed.
- R in the general formula (1) preferably has a structure selected from the following general formula group (1).
- the solubility of tetracarboxylic acid in an organic solvent is increased, and the concentration can be increased when a polyimide precursor solution is prepared. preferable.
- R ′ in the general formula (1) preferably has at least a divalent organic group selected from the following general formula group (2).
- the structure of the general formula (1) can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (3) with a diamine represented by the following general formula (4).
- R ′ represents a divalent organic group.
- R ′ represents a divalent organic group.
- the tetracarboxylic dianhydride represented by the general formula (3) 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis (4-hydroxyphenyl) ) Propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride, 2,3,3 ', 4-biphenyltetracarboxylic dianhydride, 5- (2
- the diamine represented by the general formula (4) preferably has a structure containing at least a divalent organic group selected from the following general formula group (2) as the structure of R ′.
- R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group.
- M represents an integer of 1 to 40, and n represents an integer of 1 to 20.
- R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms.
- R ′ structure is represented by the following general formula group (5).
- R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group
- m represents an integer of 1 to 40
- n represents an integer of 1 to 20
- R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms.
- R 1 and R 2 each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group.
- M represents an integer of 1 to 40, and n represents an integer of 1 to 20.
- R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms.
- the structure of the silicon diamine used in the present invention is preferably one in which R 1 and R 2 are a methyl group, an ethyl group, and a phenyl group, m is 1 to 40, and n is 2 or more. With such a structure, the solute concentration can be dissolved at a high concentration.
- R 3 is preferably a heptamethylene group, a hexamethylene group, a pentamethylene group, a tetramethylene group, or a trimethylene group, and o and p are each independently an integer of 1 to 30.
- Such a structure is preferable because flexibility can be imparted to the polyimide resin and adhesion with the substrate is improved.
- R ′′ ′′ represents a divalent organic group.
- the diamine represented by the general formula (5) is a structure containing at least a divalent organic group selected from the following general formula group (7) as the structure of R ′′ ′′.
- the amount of the combined use is 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.5 or less when the diamine mole number of the general formula (4) is 1. This is preferable because it improves the solubility of the imidized tetracarboxylic acid of the general formula (1) in an organic solvent and the imidization temperature at the time of imidization can be imidized at a low temperature.
- Method 1 In a solution in which the tetracarboxylic dianhydride represented by the general formula (3) is dispersed or dissolved in an organic solvent, the diamine represented by the general formula (4) or the general formula (4) A polyamic acid solution is prepared by adding and reacting both diamines of general formula (5). At this time, the total amount of diamine added is 0.20 to 0.80 moles per mole of tetracarboxylic dianhydride. After the reaction between the tetracarboxylic dianhydride and the diamine is completed, the resulting polyamic acid solution is heated to 100 ° C. or higher and 300 ° C. or lower, more preferably 150 ° C. or higher and 250 ° C. or lower to perform imidization.
- water is added to the polyimide resin solution and heated at 40 ° C. or higher and 200 ° C. or lower, more preferably 60 ° C. or higher and 150 ° C. or lower, so that the carboxylic acid anhydrides at both ends are heated. Can be ring-opened to obtain a partially imidized polyimide resin.
- the solvent which can be heated to the glass transition temperature or more of the polyimide resin as the solvent used in this method, and it is particularly preferable to use a solvent which can be heated to a temperature higher by 30 ° C. than the glass transition temperature. It is preferable.
- Method 2 In a solution in which the tetracarboxylic dianhydride represented by the above general formula (3) is dispersed or dissolved in an organic solvent, the diamine represented by the general formula (4) or the general formula (4) A polyamic acid solution is prepared by adding and reacting both diamines of general formula (5). At this time, the addition amount of diamine is 0.20 to 0.80 mol per 1 mol of tetracarboxylic dianhydride to prepare a polyamic acid solution.
- an imidization catalyst preferably tertiary amines such as pyridine, picoline, isoquinoline, trimethylamine, triethylamine, tributylamine, etc.
- a dehydrating agent acetic anhydride, etc.
- Method 3 In a solution in which the tetracarboxylic dianhydride represented by the above general formula (3) is dispersed or dissolved in an organic solvent, the diamine represented by the general formula (4) or the general formula (4) A polyamic acid solution is prepared by adding and reacting both diamines of general formula (5). At this time, the addition amount of diamine is 0.20 to 0.80 mol per 1 mol of tetracarboxylic dianhydride to prepare a polyamic acid solution. The polyamic acid solution is placed in a vacuum oven heated to 100 ° C. or more and 250 ° C. or less, and imidation is performed by drawing a vacuum while heating and drying. The imidized resin can be heated in water to open the terminal anhydrous ring to obtain a tetracarboxylic acid.
- the above method is preferably used. Regardless of the above method, any method can be used as long as it can obtain an imidized tetracarboxylic acid in which the terminal acid anhydride group is ring-opened and the center is imidized. There is no problem using the method.
- the reaction with both diamines of (5) is preferably 0.20 to 0.80 mole of diamine with respect to 1 mole of tetracarboxylic dianhydride, more preferably 0 to 1 mole with respect to 1 mole of tetracarboxylic dianhydride. .30 to 0.70 mol.
- the molecular weight of the imidized tetracarboxylic acid represented by the general formula (1) can be kept low, and an imidized tetracarboxylic acid having high solubility in an organic solvent can be obtained efficiently. become.
- the amount of water added in the final production step of the imidized tetracarboxylic acid is 1.5 times the amount of the terminal tetracarboxylic anhydride group in order to completely open the terminal acid dianhydride group. As described above, it is more preferable to open the ring by adding 2.0 times or more of water. It is preferable to include a large amount of water.
- solvent used for polymerization in the present invention examples include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and N, N-dimethylacetamide.
- Acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, halogenated Phenolic solvents such as phenol and catechol, or hexamethylphosphoramide, ⁇ -butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme ( 1,2-bi (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxy) Symmetric glycol diethers such as ethyl)
- polyimide precursor composition of the present invention may contain a tetracarboxylic acid represented by the following general formula (6).
- the tetracarboxylic acid may be prepared by preparing a tetracarboxylic acid represented by the general formula (6) in advance and adding it during preparation of the polyimide precursor solution, or a partial imide represented by the general formula (1). During the preparation of the converted tetracarboxylic acid solution, the tetracarboxylic acid represented by the general formula (6) can be simultaneously prepared by adding an excess of tetracarboxylic dianhydride.
- the diamine of the general formula (5) are reacted at a ratio of 0.5 mol or less to the imidized tetracarboxylic acid finally obtained, the tetramer represented by the above general formula (6) Carboxylic acid will coexist. However, depending on the reaction process, it may occur even when an amount of 0.5 mol or more is added.
- tetracarboxylic acid represented by the general formula (6) examples include 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, pyromellitic acid, and 3,3 ′, 4,4′-oxydiphthalic acid.
- the isocyanate compound used in the present invention is a compound having two or more isocyanate groups.
- isocyanate compounds include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, tetramethylxylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate.
- aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, tetramethylxylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate.
- Diisocyanates such as alicyclic diisocyanates such as isophorone diisocyanate and norbornene diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate.
- the isocyanate compounds suitably used in the present invention are aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, and tetramethylxylene diisocyanate.
- a blocked isocyanate compound or the like obtained by stabilizing the above isocyanate compound with a blocking agent can be used.
- the blocked isocyanate compound is a compound that is inactive at room temperature, and is heated to dissociate a blocking agent such as oximes, diketones, phenols, caprolactams, and regenerate isocyanate groups.
- a blocking agent such as oximes, diketones, phenols, caprolactams, and regenerate isocyanate groups.
- the blocked isocyanate compound suitably used in the present invention is a block isocyanate compound such as hexamethylene diisocyanate type isocyanurate type, biuret type, adduct type, etc., hydrogenated diphenylmethane diisocyanate type, water having a dissociation temperature of the blocking agent of 160 ° C. or less. It is an additive xylylene diisocyanate block isocyanate compound.
- the above-mentioned blocked isocyanate compound because the cured film obtained when the polyimide precursor composition is cured can be provided with high adhesion to the substrate.
- the diamine used in the present invention is a compound having two amino groups represented by the following general formula (2).
- R ′′ represents a divalent organic group.
- the diamine that can be suitably used together with the isocyanate compound is preferably a divalent organic group in which R ′′ is selected from the following general formula group (3).
- the glass transition temperature of the material is preferably 50 ° C. or higher.
- raw materials include p-phenylenediamine, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4 ′.
- the diamine because high heat resistance can be imparted to the cured film obtained when the polyimide precursor composition is cured.
- the addition amount of the isocyanate compound is expressed by the general formula (4) with respect to 1 mol of tetracarboxylic dianhydride used in the production method of the general formula (1).
- the total amount of diamine combined with both of the diamines of general formula (4) and general formula (5), or the total diamine amount when combined with the diamine shown in general formula (2) The total ratio of diamine and isocyanate compound present in the final polyimide precursor composition is 0.70 mol to 1.30 mol, more preferably 0.80 to 1.10 mol, particularly preferably The amount is 0.90 to 1.10.
- the temperature at which the isocyanate compound is added is not limited as long as imidization does not proceed, and mixing at 100 ° C. or lower, more preferably 80 ° C. or lower is preferable.
- ⁇ Preparation method of polyimide precursor composition solution It describes about the preparation method of the polyimide precursor composition solution of this invention.
- the solution is used as it is, and an isocyanate compound is added to the solution to obtain a polyimide precursor composition solution.
- the polyimide precursor composition once separated as a solid is preferably diluted with a solvent and used.
- the solvent used is preferably one or a mixture of two or more of the solvents described as the solvent used in the above polymerization.
- the solute concentration is preferably 40 to 90% by weight as the concentration of the polyimide precursor composition solution, particularly preferably 45 to 85% by weight.
- the solute concentration of the present invention is a value calculated from the following calculation formula 1.
- Solute concentration (%) solute weight / (solute weight + solvent weight) ⁇ 100 Formula 1.
- the solute weight and solvent weight in the formula are raw material weights other than the solvent dissolved in the organic solvent. For example, a certain amount (A gram) of the resin solution is taken out and heated to a temperature at which the solvent can be volatilized or left. The weight (B gram) of the solid content is measured, the weight of the solid content (B gram) is the solute weight, and the value calculated by the following calculation formula 2 is the solvent weight.
- Solvent weight AB Formula 2.
- the concentration of the solution in which the polyimide precursor composition in the present invention is dissolved is preferably 40 to 90% by weight, more preferably 45 to 85% by weight.
- the solvent removal amount is reduced, the handleability is improved, and the coating film thickness when being molded into a film body is dried.
- the amount of change in film thickness is reduced, and formability is significantly improved.
- the viscosity of a polyimide precursor composition solution can be controlled in the optimal range, it is preferable.
- a polyimide precursor composition solution when applied and dried to produce a film-shaped molded body, it depends on the coating method, but is usually preferably 6000 poise or less at 23 ° C., more preferably 5000 poise or less. . If the viscosity exceeds 6000 poise, coating may be difficult. In the present invention, it is possible to freely control from high viscosity to low viscosity by adjusting the concentration.
- polyimide precursor solution of the present invention other known materials such as organic silanes, pigments, conductive carbon black and fillers such as metal particles, abrasives, dielectrics, lubricants, etc. may be used as necessary. Additives can be added as long as the effects of the present invention are not impaired. In addition, other polymers and solvents such as water-insoluble ethers, alcohols, ketones, esters, halogenated hydrocarbons, hydrocarbons and the like can be added as long as the effects of the present invention are not impaired.
- a polyimide precursor composition solution is obtained by a known method such as a conventionally known spin coating method, spray coating method, screen printing method, dipping method, curtain coating method, dip coating method, or die coating method. It is obtained by imidation after coating on the material, drying at a temperature of 250 ° C. or less to remove the solvent.
- the polyimide precursor composition of the present invention has a low temperature required for imidization and can be cured at 250 ° C. or lower. In addition, when it can harden
- a particularly preferable curing temperature is preferably 200 ° C. or lower, and the polyimide precursor composition of the present invention also supports curing at a low temperature of 200 ° C. or lower.
- a photosensitive resin composition is mentioned as an example of utilization of the polyimide precursor composition of this invention.
- the photosensitive resin composition will be described in detail.
- it cannot be overemphasized that it is restricted to this as an example of utilization of the polyimide precursor composition of this invention.
- the composition of the photosensitive resin composition is as follows. That is, a photosensitive resin composition comprising the polyimide precursor composition, at least a photosensitive resin, and a photopolymerization initiator.
- the polyimide precursor composition used for the photosensitive resin composition if it is the said polyimide precursor composition, it can be used without specifically limiting.
- the terminal tetracarboxylic acid siloxane imide oligomer obtained by using silicon diamine is preferably used for the imidized tetracarboxylic acid, but it is limited to this. is not.
- the photosensitive resin in the present invention is a monomer, oligomer, or polymer resin that is polymerized by radicals, acids, bases, protons, amines, etc. generated by light or heat. More preferred is a resin having at least one unsaturated double bond. Further, the unsaturated double bond is an acryl group (CH 2 ⁇ CH— group), a methacryloyl group (CH 2 ⁇ C (CH 3 ) — group) or a vinyl group (—CH ⁇ CH— group). It is preferable.
- the photosensitive resin used suitably by this invention below is illustrated below, what kind of resin may be used if it is resin which has at least one said unsaturated double bond.
- the number of repeating units of EO (ethylene oxide) contained in one molecule of diacrylate or methacrylate is preferably 2 to 50, and more preferably 2 to 40.
- the solubility in an aqueous developer typified by an alkaline aqueous solution is improved, and the development time is shortened.
- the printed wiring boards when laminated on a flexible printed wiring board based on a polyimide resin, curling of the printed wiring board is prevented.
- 2-hydroxy-3-phenoxypropyl acrylate for example, 2-hydroxy-3-phenoxypropyl acrylate, monohydroxyethyl acrylate phthalate, ⁇ -carboxy-polycaprolactone monoacrylate, acrylic acid dimer, pentaerythritol tri, tetraacrylate, etc.
- Those having a hydroxyl group or a carbonyl group in the molecular structure skeleton are also preferably used.
- any photosensitive resin such as epoxy-modified acrylic resin, urethane-modified acrylic resin, or polyester-modified acrylic resin may be used.
- Photopolymerization initiator those having any structure can be used as long as they generate radicals, acids, bases, protons, amines and the like upon irradiation with light.
- the component ratio of the polyimide precursor composition, the photosensitive resin, and the photopolymerization initiator in the photosensitive resin composition is 10 parts by weight with respect to 100 parts by weight of the solid content of the polyimide precursor composition. It is preferable to add up to 200 parts by weight and the photopolymerization initiator in an amount of 0.1 to 50 parts by weight.
- the photosensitive resin When the photosensitive resin is less than the above range, the heat resistance of the cured film after photo-curing the photosensitive resin is lowered, and the contrast when exposed and developed tends to be difficult. For this reason, it is possible to set the resolution at the time of exposure / development to an optimal range by setting the value within the above range.
- the photopolymerization initiator When the photopolymerization initiator is less than the above range, the curing reaction of the photosensitive resin during light irradiation hardly occurs, and the curing may be insufficient. Moreover, when there is too much, adjustment of light irradiation amount becomes difficult and may be in an overexposure state. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust within the above range.
- the photosensitive resin composition of the present invention is excellent in heat resistance after curing (solder heat resistance, etc.), chemical resistance (alkali solution resistance, acid resistance, solvent resistance, etc.), moisture resistance environment stability, and heat resistance environment stability.
- solvent heat resistance etc.
- chemical resistance alkali solution resistance, acid resistance, solvent resistance, etc.
- moisture resistance environment stability e.g., moisture resistance environment stability
- heat resistance environment stability e.g., heat resistance environment stability
- thermosetting resin used in the photosensitive resin composition of the present invention is epoxy resin, isocyanate resin, block isocyanate resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, hydrosilyl cured resin, allyl cured resin.
- Thermosetting resins such as unsaturated polyester resins; side chain reactive group type thermosetting resins having reactive groups such as allyl group, vinyl group, alkoxysilyl group, hydrosilyl group, etc. at the side chain or terminal of the polymer chain A polymer or the like can be used.
- the thermosetting component may be used alone or in combination of two or more.
- an epoxy resin By containing an epoxy resin component, heat resistance (solder heat resistance, etc.) and chemical resistance (alkali solution resistance, acid resistance, solvent resistance, etc.) for a cured resin obtained by curing a thermosetting resin composition ), Humidity resistance environment stability and heat resistance environment stability can be imparted, and adhesion to a conductor such as a metal foil or a circuit board can be imparted.
- any resin having any structure may be used as long as it contains at least two epoxy groups in the molecule.
- bisphenol A type epoxy resin bisphenol AD type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolac type epoxy resin, water-added bisphenol A type epoxy resin, ethylene oxide adduct bisphenol A type epoxy resin, Propylene oxide adduct bisphenol A type epoxy resin, novolak type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, polyglycol type epoxy resin, cyclic aliphatic epoxy resin, Cyclopentadiene type epoxy resin, dicyclopentadiene type epoxy resin, cresol novolac type epoxy resin, glycidyl a Emission type epoxy resins, naphthalene type epoxy resins, urethane modified epoxy resins, rubber-modified epoxy resins, and epoxy resins such as epoxy
- epoxy resin examples include, for example, the product name Epicron HP-4700 of the naphthalene type tetrafunctional epoxy resin manufactured by Dainippon Ink Chemical Co., Ltd., the product name Epicron HP-7200 of the cyclopentadiene type epoxy resin, and the product of the phenol novolac type epoxy resin.
- Epicron N-740 Epicron EXA-7240, which is a high heat resistance epoxy resin
- Epicron N-660, N-665, N-670, N-680, N-655- which is a cresol novolac type polyfunctional epoxy resin
- EXP cresol novolac type polyfunctional epoxy resin
- Epicron N-740 trade name of tetraphenylethane type epoxy resin
- Epicron ETePE trade name of triphenylmethane type epoxy resin
- Epicron ETrPM trade name of Japan Epoxy Resin Co., Ltd.
- Bisphenol A ⁇ ⁇ ⁇ ⁇ type epoxy resin such as Coat 828, bisphenol F type epoxy resin such as YDF-170 trade name manufactured by Toto Kasei Co., Ltd., trade names Epicoat 152 and 154 manufactured by Japan Epoxy Resin Co., Ltd., Nippon Kayaku Co., Ltd.
- Type epoxy resin trade name Epon 1031S manufactured by Japan Epoxy Resin Co., Ltd., trade name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., trade names Denacol EX-611, EX-614, EX manufactured by Nagase Kasei Co., Ltd. -614B, EX-622, EX-512, EX-521, E Multifunctional epoxy resins such as X-421, EX-411, EX-321, trade name Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., trade name YH434 manufactured by Toto Kasei Co., Ltd., manufactured by Mitsubishi Gas Chemical Co., Ltd.
- Product name Araldite PT810 and other heterocyclic ring-containing epoxy resins, UCC's ERL4234, 4299, 4221, and 4206 alicyclic epoxy resins, etc. may be used alone or in combination of two or more. it can.
- the amount of the thermosetting resin used in the present invention is 0.5 to 100 parts by weight based on 100 parts by weight of the solid content of the polyimide precursor composition, the photosensitive resin, and the photopolymerization initiator. It is preferable to mix. More preferably, it is 1.0 to 50 parts by weight, and particularly preferably 1.0 to 10 parts by weight. It is preferable to add it in the above range since the heat resistance, chemical resistance and electrical insulation reliability of the cured film of the photosensitive resin composition can be improved. Moreover, since a softness
- the epoxy resin used in the photosensitive resin composition of the present invention can be used in combination with an epoxy compound having only one epoxy group in one molecule in addition to the above epoxy resin.
- examples include n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, dibromocresyl glycidyl ether, and the like.
- alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate are exemplified.
- the photosensitive resin composition of the present invention includes a compound having a phenolic hydroxyl group, a compound having an amine group, a compound having a carboxylic acid, a compound having a mercapto group, an isocyanate as a curing agent for the thermosetting resin.
- a compound having a group can also be used.
- phenol novolac type phenol resin cresol novolac type phenol resin
- phenol resin such as naphthalene type phenol resin, amino resins, urea resins, melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acid, and Bronsted acid salts, polymercaptan compounds, isocyanates and blocked isocyanate compounds, and the like
- phenol resin such as naphthalene type phenol resin, amino resins, urea resins, melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acid, and Bronsted acid salts, polymercaptan compounds, isocyanates and blocked isocyanate compounds, and the like
- the curing accelerator for the thermosetting resin is not particularly limited.
- phosphine compounds such as triphenylphosphine
- amine compounds such as tertiary amine, trimethanolamine, triethanolamine, and tetraethanolamine Borate compounds such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl
- Imidazoles such as imidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; Methyl imidazoline, 2-ethyl Imidazolines such as midazoline, 2-isopropylimidazoline, 2-phenylim
- urethane resin contains an amino group
- 2-ethyl-4-methylimidazole 2-phenyl-4-methylimidazole, 2,4-diamino-6-
- imidazoles such as 2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine.
- a flame retardant such as a flame retardant, an antifoaming agent, a coupling agent, a filler, an adhesion aid, a leveling agent, and a polymerization inhibitor
- fine inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, calcium carbonate, and fine organic polymer fillers may be contained. It is preferable to select the content appropriately.
- the photosensitive resin composition of the present invention is preferably used as a photosensitive resin composition solution dissolved in an organic solvent from the viewpoint of handling.
- the photosensitive resin composition of the present invention has high solubility in various organic solvents, for example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide systems such as N, N-dimethylformamide and N, N-diethylformamide.
- acetamide solvent such as N, N-dimethylacetamide, N, N-diethylacetamide
- pyrrolidone solvent such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, phenol, o-, m- or Phenolic solvents such as p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, ⁇ -butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ) Ether), Methyl Trigura (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldigig Symmetric glycol diethers such as lime
- symmetric glycol diethers are particularly preferable because the solubility of the photosensitive resin composition is high.
- the organic solvent is preferably blended in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive resin composition.
- the photosensitive resin composition of the present invention is obtained by uniformly mixing various raw materials blended in the photosensitive resin composition.
- a general kneading apparatus such as a three roll or bead mill apparatus may be used for mixing.
- the pattern can be formed as follows either directly with the photosensitive resin composition of the present invention or after preparing the photosensitive resin composition solution.
- the photosensitive resin composition is applied to a substrate and dried to remove the organic solvent.
- the substrate can be applied by screen printing, curtain roll, river roll, spray coating, spin coating using a spinner, or the like.
- the coating film (preferably having a thickness of 5 to 100 ⁇ m, particularly 10 to 100 ⁇ m) is dried at 120 ° C. or less, preferably 40 to 100 ° C.
- a negative photomask is placed on the dried coating film and irradiated with actinic rays such as ultraviolet rays, visible rays, and electron beams.
- the relief pattern can be obtained by washing out the unexposed portion with a developer using various methods such as shower, paddle, dipping or ultrasonic waves. Since the time until the pattern is exposed varies depending on the spraying pressure and flow velocity of the developing device and the temperature of the etching solution, it is preferable to find optimal apparatus conditions as appropriate.
- This developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, or N-methyl-2-pyrrolidone.
- alkaline compound that gives the alkaline aqueous solution include hydroxides, carbonates, hydrogen carbonates, amine compounds, and the like of alkali metals, alkaline earth metals, or ammonium ions, specifically sodium hydroxide.
- the aqueous solution is a compound other than this as long as it exhibits basicity can also be naturally used.
- the concentration of the alkaline compound that can be suitably used in the development step of the photosensitive resin composition of the present invention is preferably 0.01 to 20% by weight, particularly preferably 0.02 to 10% by weight.
- the temperature of the developer depends on the composition of the photosensitive resin composition and the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. Is preferably used.
- the relief pattern formed by the above development process is rinsed to remove unnecessary residues.
- the rinsing liquid include water and acidic aqueous solutions.
- a cured film rich in heat resistance can be obtained by imidizing tetracarboxylic acid and diamine that have been imidized by heat treatment.
- the cured film is determined in consideration of the wiring thickness and the like, but the thickness is preferably about 2 to 50 ⁇ m. It is desired that the final curing temperature at this time can be imidized by heating at a low temperature for the purpose of preventing oxidation of the wiring and the like and not reducing the adhesion between the wiring and the substrate.
- the imidization temperature applied at this time is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and particularly preferably 130 ° C. or higher and 190 ° C. or lower. If the final heating temperature is high, the wiring is oxidatively deteriorated, which is not preferable.
- a pattern comprising a cured film formed from the photosensitive resin composition of the present invention is excellent in heat resistance, electrical and mechanical properties, and is particularly excellent in flexibility.
- the insulating film of the present invention preferably has a thickness of about 2 to 50 ⁇ m and a resolution of at least 10 ⁇ m after photocuring, particularly a resolution of about 10 to 1000 ⁇ m. Therefore, the insulating film of the present invention is particularly suitable as an insulating material for a high-density flexible substrate. Furthermore, it is used for various photo-curing wiring coating protective agents, photosensitive heat-resistant adhesives, electric wire / cable insulation coatings, and the like.
- the polyimide precursor composition of the present invention is excellent in low-temperature processability, and the printed wiring board (including a flexible printed wiring board) made of a resin such as a polyimide resin, an epoxy resin, or an aramid resin as a base material, for example. It can be preferably used as a wiring coating protective agent for protecting the surface of the substrate as a base material, a wiring coating protective agent for electric wires and cables, a heat-resistant interlayer adhesive when laminating a flexible printed wiring board, and the like. In particular, since it has excellent electrical insulation reliability, it is used as a wiring coating protective agent for printed wiring boards.
- Example 1 200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 158 g of 1,2-bis (2-methoxyethoxy) ethane and heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KF8010, molecular weight 830, silicon diamine of the following general formula (7),
- the solution was cooled to room temperature and charged with 40.1 g (0.230 mol) of tolylene diisocyanate (a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate) at room temperature. Were mixed uniformly for 1 hour to obtain a polyimide precursor composition solution.
- the solute concentration of this solution was 70% by weight, and the viscosity of the solution was 220 poise at 23 ° C.
- the container was allowed to stand for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured.
- the viscosity at that time was 220 poise at 23 ° C., and it was revealed that the viscosity was not changed and could be stored at room temperature for a long time.
- Adhesiveness of coating film The adhesive strength of this polyimide film was evaluated by a cross-cut tape method according to JIS K5400. ⁇ The one that does not peel off by the cross-cut tape method ⁇ , if more than half of the cells remain The case where the residual amount of the squares was less than half was marked with x.
- Example 2 200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 122 g of 1,2-bis (2-methoxyethoxy) ethane and heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KF8010, molecular weight 830, silicon diamine of the following general formula (7),
- a blocked isocyanate compound manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: trade name Takenate B-815N, hydrogenated diphenylmethane diisocyanate block isocyanate, solid content: 60%, NCO content: 7.3%) 132 g (0.230 mol) was added and stirred uniformly at room temperature for 1 hour to obtain a polyimide precursor composition solution.
- the solution had a solute concentration of 70% by weight and a solution viscosity of 200 poise at 23 ° C.
- Example 3 200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride was dispersed in 140 g of 1,2-bis (2-methoxyethoxy) ethane and heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KF8010, molecular weight 830, silicon diamine of the following general formula (7),
- a blocked isocyanate compound manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: trade name Takenate B-815N, hydrogenated diphenylmethane diisocyanate block isocyanate, solid content: 60%, NCO content: 7.3%) 60.0 g (0.115 mol) and 20.0 g (0.115 mol) of tolylene diisocyanate (a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate) were charged at room temperature. Were mixed uniformly for 1 hour to obtain a polyimide precursor composition solution. The solution had a solute concentration of 70% by weight and a solution viscosity of 210 poise at 23 ° C.
- Example 4 200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride was dispersed in 179 g of 1,2-bis (2-methoxyethoxy) ethane and heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (trade name X-22-9409S, molecular weight 1492, silicon diamine of the following general formula (7),
- 172 g (0.115 mol) was added, and uniform stirring was performed for 30 minutes.
- the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours.
- the mixture was cooled to room temperature and 27.7 g (1.54 mol) of water was added. After stirring uniformly for 30 minutes, the mixture was heated to 80 ° C. and refluxed for 3 hours.
- Example 5 40.0 g (0.112 mol) of 4,4′-diphenylsulfonetetracarboxylic dianhydride was dispersed in 64.1 g of 1,2-bis (2-methoxyethoxy) ethane and kept at 20 ° C.
- Silicon diamine siloxane diamine
- trade name KF8010 molecular weight 830, silicon diamine of the following general formula (7)
- the solution was then cooled to room temperature and charged with 9.8 g (0.056 mol) of tolylene diisocyanate (a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate) at room temperature. Were mixed uniformly for 1 hour to obtain a polyimide precursor composition solution. The solute concentration of this solution was 60% by weight, and the viscosity of the solution was 8 poise at 23 ° C.
- tolylene diisocyanate a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate
- Example 6 20.0 g (0.0645 mol) of 4,4′-oxydiphthalic dianhydride was dispersed in 32.1 g of 1,2-bis (2-methoxyethoxy) ethane and kept at 20 ° C.
- Silicon diamine siloxane diamine
- trade name KF8010 molecular weight 830, silicon diamine of the following general formula (7)
- the solution was then cooled to room temperature and charged with 6.7 g (0.0387 mol) of tolylene diisocyanate (a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate) at room temperature. Were mixed uniformly for 1 hour to obtain a polyimide precursor composition solution.
- the solution had a solute concentration of 60% by weight and a solution viscosity of 5 poise at 23 ° C.
- Example 7 Disperse 300 g (0.576 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride in 421 g of 1,2-bis (2-methoxyethoxy) ethane, and Kept.
- Polycarbonate diol bis (4-aminobenzoate) (a diamine represented by the following general formula (8):
- R 3 is a hexamethylene group
- R 4 is a pentamethylene group
- o, p 1 to 20
- 272 g (0.231 mol) of molecular weight 1180) is added, and the mixture is stirred uniformly for 30 minutes. It was. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and 27.7 g (1.54 mol) of water was added. After stirring uniformly for 30 minutes, the mixture was heated to 80 ° C. and refluxed for 3 hours. A solution in which the imidized tetracarboxylic acid was dissolved was obtained.
- the solution was then cooled to room temperature and charged with 60.1 g (0.345 mol) of tolylene diisocyanate (a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate) at room temperature. Were mixed uniformly for 1 hour to obtain a polyimide precursor composition solution.
- the solution had a solute concentration of 60% by weight and a solution viscosity of 180 poise at 23 ° C.
- Example 8 300 g (0.576 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride was dispersed in 396 g of 1,2-bis (2-methoxyethoxy) ethane, and the mixture was heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KF8010, molecular weight 830, silicon diamine of the following general formula (7),
- the solution had a solute concentration of 70% by weight, and the viscosity of the solution became a high-viscosity elastic body at 10000 poise at 23 ° C. Even when this solution was diluted to a solute concentration of 20% by weight, it became a very viscous solution of 6000 poise at 23 ° C., and the physical property value could not be evaluated.
- the photosensitive resin composition was first mixed with a general stirring device equipped with a stirring blade, and the solution was passed twice with a three-roll mill to obtain a uniform solution.
- the following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device. The evaluation results are shown in Table 4.
- a photomask with 10 lines left) was placed and exposed to UV light at 300 mJ / cm 2 in a nitrogen atmosphere.
- This photosensitive film was subjected to spray development for 30 seconds at a discharge pressure of 1.0 kgf / mm 2 using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. After development, the film was thoroughly washed with pure water, and then dried by heating in an oven at 170 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.
- Coating film adhesion The adhesive strength of the cured film of the photosensitive resin composition obtained in the above item (Preparation of coating film on polyimide film) was evaluated by a cross-cut tape method according to JIS K5400. ⁇ The one that does not peel off by the cross-cut tape method ⁇ , if 95% or more of the cells remain The case where the residual amount of the mesh was less than 80% was evaluated as x.
- solvent resistance The solvent resistance of the cured film of the photosensitive resin composition obtained in the above item (preparation of coating film on polyimide film) was evaluated. In the evaluation method, the film was dipped in isopropanol at 25 ° C. for 15 minutes and then air-dried to observe the state of the film surface. ⁇ : There is no abnormality in the coating film. X: Abnormality occurs in the coating film.
- the acid resistance of the cured film of the photosensitive resin composition obtained in the above item was evaluated.
- the film was immersed in a 2N hydrochloric acid solution at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
- ⁇ The coating film has no abnormality (whitening or peeling).
- X Abnormality (whitening or peeling) occurs in the coating film.
- Alkali resistance The alkali resistance of the cured film of the photosensitive resin composition obtained in the above item (preparation of coating film on polyimide film) was evaluated. In the evaluation method, the film was dipped in a 2N sodium hydroxide solution at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed. ⁇ : There is no abnormality (whitening or peeling) in the coating film. X: Abnormality (whitening or peeling) occurs in the coating film.
- a cured film laminated film of a photosensitive resin composition was prepared on the surface of a 25 ⁇ m-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the above item (Preparation of a coating film on a polyimide film).
- the cured film laminated film was cut into a 30 mm ⁇ 10 mm strip, bent 10 times at 180 ° at 15 mm, and the coating film was visually confirmed to check for cracks.
- ⁇ The cured film has no cracks.
- ⁇ The cured film has some cracks.
- X The cured film has cracks.
- a comb-shaped pattern of line width / space width 100 ⁇ m / 100 ⁇ m on a flexible copper-laminated laminate (copper foil thickness 12 ⁇ m, polyimide film is Apical 25 NPI manufactured by Kaneka Corporation, and copper foil is bonded with a polyimide adhesive) After being prepared and immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, the surface of the copper foil was treated by washing with pure water. Then, the cured film of the photosensitive resin composition was produced on the comb pattern by the method similar to the production method of the cured film on a polyimide film, and the test piece was adjusted.
- a 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
- ⁇ A resistance value of 10 6 or more in 500 hours after the start of the test, and no occurrence of migration or dendrite.
- X Migration, dendrite, etc. occurred in 500 hours after the start of the test.
- Example 9 Example 9 except that 5 parts by weight of an epoxy resin (Epicron N-665, which is a cresol novolac type polyfunctional epoxy resin) was added to 100 parts by weight of the solid content of the photosensitive resin composition of Example 9 above.
- the evaluation was performed in the same manner as above. Further, as a solder heat resistance test, evaluation was performed by the following evaluation method. The evaluation results are shown in Table 4.
- the photosensitive resin composition solution is cast and applied to an area of 100 mm ⁇ 100 mm on a 75 ⁇ m polyimide film (manufactured by Kaneka Corporation: product name 75 NPI) using a Baker type applicator so that the final dry thickness is 25 ⁇ m.
- a negative photomask having a completely transparent area of 50 mm ⁇ 50 mm was placed and exposed to UV light at 300 mJ / cm 2 in a nitrogen atmosphere.
- This photosensitive film was subjected to spray development for 30 seconds at a discharge pressure of 1.0 kgf / mm 2 using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C.
- Example 14 Example 9 except that 5 parts by weight of an epoxy resin (Epicron N-665, which is a cresol novolac type polyfunctional epoxy resin) was added to 100 parts by weight of the solid content of the photosensitive resin composition of Example 10 above. The evaluation was performed in the same manner as above. Furthermore, as a solder heat resistance test, evaluation was performed by the same evaluation method as in Example 13. The evaluation results are shown in Table 4.
- an epoxy resin Epon N-665, which is a cresol novolac type polyfunctional epoxy resin
- Example 7 A photosensitive resin composition solution was prepared in the same manner as in Example 9 except that the half-esterified compound obtained in Synthesis Example 5 was used, and evaluation was performed in the same manner as in Example 9. The evaluation results are shown in Table 5. The imidization did not proceed sufficiently, and the moisture resistance insulation was very poor.
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Abstract
Description
少なくとも下記一般式(1)
に示すイミド化したテトラカルボン酸と、イソシアネート系化合物とを含むことを特徴とする、ポリイミド前駆体組成物である。
に示すジアミンを含むことを特徴とする、ポリイミド前駆体組成物であることが好ましい。
で示される2価の有機基を少なくとも含むことが好ましい。
より選ばれる2価の有機基であることが好ましい。
に示すテトラカルボン酸二無水物と、
下記一般式(4)
に示すジアミンとを、
一般式(3)に示すテトラカルボン酸二無水物1モルに対して一般式(4)に示すジアミン0.20~0.80モルの比率で反応を行いアミド酸を得る工程、
前記アミド酸をイミド化し、イミドを得る工程、及び
前記イミドに水を反応させて、内部がイミド化しており、末端がテトラカルボン酸である、イミド化したテトラカルボン酸を得る工程を含み、
さらに、前記工程で得たイミド化したテトラカルボン酸と、イソシアネート系化合物とを、イミド化したテトラカルボン酸1モルに対して、イソシアネート系化合物を、前記アミド酸を得る工程で用いた一般式(4)に示すジアミンとあわせた合計の比率が、0.70モル~1.30モルとなる比率で、混合する工程を含むことを特徴とする、ポリイミド前駆体組成物の製造方法である。
で示されるジアミンを少なくとも含むことが好ましい。
に示すイミド化したテトラカルボン酸と、イソシアネート系化合物とを含有することを特徴とするポリイミド前駆体組成物である。本願発明のポリイミド前駆体組成物とは上記一般式(1)の構造体及びイソシアネート系化合物を含有するものであるが、それぞれが共有結合を有していないものを示す。つまり、一般的なポリイミド前駆体組成物とは、例えば上記一般式(1)及び芳香族ジアミンが一部アミド結合で共有結合したポリマーを示すが、本願発明の上記ポリイミド前駆体組成物は一般式(1)及びイソシアネート系化合物が共有結合を有しないものを示す。このように共有結合を有しないポリイミド前駆体組成物とすることで上記一般式(1)及びイソシアネート系化合物を溶解した溶液の濃度を高めることが可能となり、溶液の粘度の変化(分子量変化)が生じにくくできる。
イミド化したテトラカルボン酸とは、下記一般式(1)
で示されるように、構造式中に少なくとも2つのイミド結合を有しており、末端がテトラカルボン酸になっている構造を持つテトラカルボン酸である。また、本願発明のイミド化したテトラカルボン酸は、分子量が短い程、有機溶剤溶液への溶解度が向上するので好ましい。例えば、オリゴマーと呼ばれる、比較的分子量の低い重合体であることが好ましい。このようなテトラカルボン酸構造とすることでイミド化しているにも係らず、溶剤への溶解性を高めることができる。また、構造中の結合がアミド結合ではなく、イミド結合となっているので、貯蔵安定性に優れる。その為、ポリイミド前駆体組成物の溶液を調整した際に溶液粘度の経時劣化を防ぎ、粘度変化を抑えることができる。
より具体的には、上記一般式(3)で表されるテトラカルボン酸二無水物としては、3,3’,4,4’―ベンゾフェノンテトラカルボン酸二無水物、ピロメリット酸二無水物、3,3’,4,4’―オキシジフタル酸二無水物、2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物、2,2-ビス(4-ヒドロキシフェニル)プロパンジベンゾエート-3,3´,4,4´-テトラカルボン酸二無水物、3,3’,4,4’―ジフェニルスルホンテトラカルボン酸二無水物、3,3’,4,4’―ビフェニルテトラカルボン酸二無水物、2,3,3’,4―ビフェニルテトラカルボン酸二無水物、5-(2,5-ジオキソテトラヒドロ-3-フラニル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物を用いることが好ましく、特に好ましくは、2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物、3,3’,4,4’―ジフェニルスルホンテトラカルボン酸二無水物、3,3’,4,4’―オキシジフタル酸二無水物、5-(2,5-ジオキソテトラヒドロ-3-フラニル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物を用いることがポリイミド前駆体の溶解性を向上させるとともに、ポリイミド樹脂の耐薬品性を向上させる上で好ましい。中でも特に、溶解性を向上させフィルムの特性を向上させる上で、2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物を用いることが好ましい。
上記構造骨格を持たせることで、ポリイミド樹脂に成形した際に、ポリイミド樹脂の被膜に柔軟性を付与できると共に、ポリイミド樹脂に成形する際のイミド化温度を低下させることができる。この構造骨格を併用することでポリイミド樹脂のイミド化温度を250℃以下に低下させることがより可能となる。
上記構造を使用することで、ポリイミド被膜に柔軟性を付与できると共に、イミド化温度を低下させ、溶質濃度を高濃度に調整できる共に、基材との密着性が向上するので好ましい。
中でも、特に基材との密着性を考慮した場合、上記構造中、下記一般式群(6)であることが好ましい。
特に本願発明に用いられるシリコンジアミンの構造は、R1,R2がメチル基、エチル基、フェニル基であって、mは1~40、nが2以上であるものが好ましく用いられる。このような構造にすることで溶質濃度を高濃度に溶解することができる。
また、R3はへプタメチレン基、ヘキサメチレン基、ペンタメチレン基、テトラメチレン基、トリメチレン基であって、o及びpは、それぞれ独立して、1~30の整数である構造が好ましく用いられる。
また、一般式(5)で示されるジアミンとしては、より具体的には、R’’’’の構造として少なくとも下記一般式群(7)より選ばれる2価の有機基を含む構造である。
上記一部イミド化したテトラカルボン酸の製造方法としては、種々の方法が挙げられる。
上記テトラカルボン酸は、一般式(6)で示されるテトラカルボン酸を予め作製しておいてポリイミド前駆体溶液の調整中に添加する方法や、上記一般式(1)で示される、一部イミド化したテトラカルボン酸溶液の作製中において、過剰にテトラカルボン酸二無水物を添加することで上記一般式(6)で示されるテトラカルボン酸を同時に作製することもできる。つまり、上記一般式(1)の製造工程において、一般式(3)で示されるテトラカルボン酸二無水物1モルに対して、一般式(4)で示されるジアミン、もしくは、一般式(4)と一般式(5)のジアミンの両方の総ジアミン量が0.5モル以下の比率で反応させた場合に、最終得られるイミド化したテトラカルボン酸に、上記一般式(6)で示されるテトラカルボン酸が共存することになる。ただし、反応の過程によっては0.5モル以上の量を添加した場合においても生じる場合がある。
本願発明で用いられるイソシアネート系化合物とは、イソシアネート基を2つ以上有する化合物である。
本願発明で用いられるジアミンとは、下記一般式(2)で示される、アミノ基を2つ有する化合物である。
本願発明において、イソシアネート系化合物とともに好適に用いることのできるジアミンは、式中のR''が下記一般式群(3)より選ばれる2価の有機基であることが好ましい。
本発明のポリイミド前駆体組成物溶液の調製方法について記載する。イミド化したテトラカルボン酸を合成した溶液中でポリイミド前駆体組成物溶液を調整する場合には、そのままその溶液を用いて、その溶液にイソシアネート系化合物を投入してポリイミド前駆体組成物溶液を得ることが好ましく、一度、固形として分離したポリイミド前駆体組成物については、溶剤で希釈して用いることが好ましい。
本願発明のポリイミド前駆体組成物の利用の1例として、感光性樹脂組成物が挙げられる。以下において、感光性樹脂組成物について詳述する。なお、本願発明のポリイミド前駆体組成物の利用の例としては、これに限られることは言うまでもない。感光性樹脂組成物の構成は、次のとおりである。すなわち、上記ポリイミド前駆体組成物と、少なくとも感光性樹脂、及び、光重合開始剤を含有することを特徴とする感光性樹脂組成物である。なお、感光性樹脂組成物に使用するポリイミド前駆体組成物については、上記ポリイミド前駆体組成物であれば、特に限定する事無く使用可能である。ポリイミド前駆体組成物の内、イミド化したテトラカルボン酸の方については、シリコンジアミン(シロキサンジアミン)を用いて得られる、末端テトラカルボン酸シロキサンイミドオリゴマーが好ましく用いられるが、これに限定されるものではない。
本願発明における感光性樹脂とは、光もしくは熱によって発生したラジカル、酸、塩基、プロトン、アミン等によって、重合するモノマー、オリゴマーもしくは高分子樹脂である。より好ましくは、少なくとも不飽和二重結合を1つ有する樹脂である。さらには、前記不飽和二重結合は、アクリル基(CH2=CH-基)、メタアクリロイル基(CH2=C(CH3)-基)もしくはビニル基(-CH=CH-基)であることが好ましい。下記に本願発明で好適に用いられる感光性樹脂を例示するが、上記不飽和二重結合を少なくとも1つ有する樹脂であればどのような樹脂を用いても良い。
光重合開始剤としては、光の照射により、ラジカル、酸、塩基、プロトン、アミン等を発生するものであればどのような構造のものも使用することができる。例えば、ミヒラ-ズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、4,4’,4’’-トリス(ジメチルアミノ)トリフェニルメタン、2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニル-1,2’-ジイミダゾール、アセトフェノン、ベンゾイン、2-メチルベンゾイン、ベンゾインメチルエ-テル、ベンゾインエチルエ-テル、ベンゾインイソプロピルエ-テル、ベンゾインイソブチルエ-テル、2-t-ブチルアントラキノン、1,2-ベンゾ-9,10-アントラキノン、メチルアントラキノン、チオキサントン、2,4-ジエチルチオキサントン、2-イソプロピルチオキサントン、1-ヒドロキシシクロヘキシルフェニルケトン、ジアセチルベンジル、ベンジルジメチルケタ-ル、ベンジルジエチルケタ-ル、2(2’-フリルエチリデン)-4,6-ビス(トリクロロメチル)-S-トリアジン、2[2’(5’’-メチルフリル)エチリデン]-4,6-ビス(トリクロロメチル)-S-トリアジン、2(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-S-トリアジン、2,6-ジ(p-アジドベンザル)-4-メチルシクロヘキサノン、4,4’-ジアジドカルコン、ジ(テトラアルキルアンモニウム)-4,4’-ジアジドスチルベン-2,2’-ジスルフォネ-ト、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタン-1、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルフォスフィンオキサイド、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-ケトン、ビス(n5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム、1,2-オクタノンジオン,1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、ヨード二ウム,(4-メチルフェニル)[4-(2-メチルプロピル)フェニル]-ヘキサフルオロフォスフェート(1-)、エチル-4-ジメチルアミノベンゾエート、2-エチルヘキシル-4-ジメチルアミノベンゾエート、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシオム)などが挙げられる。上記光重合開始剤は適宜選択することが好ましく、1種以上を混合させて用いることが好ましい。
本願発明の感光性樹脂組成物は、硬化後の耐熱性(半田耐熱性等)、耐薬品性(アルカリ溶液耐性、耐酸性、耐溶剤性等)、耐湿環境安定性、耐熱環境安定性に優れる樹脂組成物にするために、熱硬化性樹脂を配合することが好ましい。
この発明の感光性樹脂組成物には、さらに必要に応じて難燃剤、消泡剤、カップリング剤、充填剤、接着助剤、レベリング剤、重合禁止剤等の各種添加剤を加えることができる。充填剤としては、シリカ、マイカ、タルク、硫酸バリウム、ワラストナイト、炭酸カルシウムなどの微細な無機充填剤、微細な有機ポリマ-充填剤を含有させてもよい。含有量は適宜選定することが好ましい。
本願発明の感光性樹脂組成物は、取扱いの観点から有機溶剤に溶解した感光性樹脂組成物溶液として用いることが好ましい。本願発明の感光性樹脂組成物は、種々の有機溶剤に溶解性が高く、例えば、ジメチルスルホキシド、ジエチルスルホキシドなどのスルホキシド系溶媒、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミドなどのホルムアミド系溶媒、N,N-ジメチルアセトアミド、N,N-ジエチルアセトアミドなどのアセトアミド系溶媒、N-メチル-2-ピロリドン、N-ビニル-2-ピロリドンなどのピロリドン系溶媒、フェノール、o-、m-またはp-クレゾール、キシレノール、ハロゲン化フェノール、カテコールなどのフェノール系溶媒、あるいはヘキサメチルホスホルアミド、γ-ブチロラクトン、メチルモノグライム(1,2-ジメトキシエタン)、メチルジグライム(ビス(2-メトキシエテル)エーテル)、メチルトリグライム(1,2-ビス(2-メトキシエトキシ)エタン)、メチルテトラグライム(ビス[2-(2-メトキシエトキシエチル)]エーテル)、エチルモノグライム(1,2-ジエトキシエタン)、エチルジグライム(ビス(2-エトキシエチル)エーテル)、ブチルジグライム(ビス(2-ブトキシエチル)エーテル)等の対称グリコールジエーテル類、γ―ブチロラクトンやN-メチル-2-ピロリドン、メチルアセテート、エチルアセテート、イソプロピルアセテート、n―プロピルアセテート、ブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート(別名、カルビトールアセテート、酢酸2-(2-ブトキシエトキシ)エチル))、ジエチレングリコールモノブチルエーテルアセテート、3-メトキシブチルアセテート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールジアセテート、1,3―ブチレングリコールジアセテート等のアセテート類や、ジプロピレングリコールメチルエーテル、トリプロピレングリコールメチルエーテル、プロピレングリコールn-プロピルエーテル、ジプロピレングリコールn-プロピルエーテル、プロピレングリコールn-ブチルエーテル、ジプロピレングリコールn-ブチルエーテル、トリピレングリコールn-プロピルエーテル、プロピレングリコールフェニルエーテル、ジプロピレングリコールジメチルエーテル、1,3―ジオキソラン、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールものエチルエーテル等のエーテル類の溶剤を用いることもできる。尚、必要に応じて低沸点のヘキサン、アセトン、トルエン、キシレン等を用いて感光性樹脂組成物溶液とすることができる。
この発明の感光性樹脂組成物は、上記感光性樹脂組成物に配合される各種原料を均一に混合して得られる。均一に混合する方法としては、例えば3本ロール、ビーズミル装置等の一般的な混練装置を用いて混合すればよい。また、溶液の粘度が低い場合には、一般的な攪拌装置を用いて混合してもよい。
この発明の感光性樹脂組成物を直接に、もしくは、上記感光性樹脂組成物溶液を調整した後に、以下のようにしてパタ-ンを形成することができる。先ず上記の感光性樹脂組成物を基板に塗布し、乾燥して有機溶媒を除去する。基板への塗布はスクリ-ン印刷、カ-テンロ-ル、リバ-スロ-ル、スプレーコーティング、スピンナーを利用した回転塗布等により行うことができる。塗布膜(好ましくは厚み:5~100μm、特に10~100μm)の乾燥は120℃以下、好ましくは40~100℃で行う。乾燥後、乾燥塗布膜にネガ型のフォトマスクを置き、紫外線、可視光線、電子線などの活性光線を照射する。次いで、未露光部分をシャワー、パドル、浸漬または超音波等の各種方式を用い、現像液で洗い出すことによりレリ-フパタ-ンを得ることができる。なお、現像装置の噴霧圧力や流速、エッチング液の温度によりパターンが露出するまでの時間が異なる為、適宜最適な装置条件を見出すことが好ましい。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン158gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
上記ポリイミド前駆体組成物溶液を用いて、ベーカー式アプリケーターを用いて、75μmのポリイミドフィルム(株式会社カネカ製:商品名75NPI)に最終乾燥厚みが25μmになるように流延・塗布し、120℃で1時間乾燥した後、窒素雰囲気下160℃で30分加熱してイミド化を行った。
このポリイミドフィルムの接着強度をJIS K5400に従って碁盤目テープ法で評価した。
碁盤目テープ法で剥がれの無いものを○、
升目の半分以上が残存している場合を△、
升目の残存量が半分未満のものを×とした。
ポリイミドフィルムのイミド化が充分でないと、環境試験装置内での安定性が低下する。そのため、環境試験装置内での安定性を測定した。
環境試験装置は、エスペック株式会社製恒温高湿器 型式:PR-1Kを用いて85℃/85%RH 1000時間試験後のポリイミドフィルム上の塗膜の状態で判断した。
ポリイミド樹脂が変化無いものを〇、
ポリイミド樹脂が一部溶解しているものを△、
ポリイミド樹脂が完全に溶解しているもの×とした。
ポリイミドフィルム表面の耐薬品性の評価を行った。評価方法は下記評価項目1~3の評価条件でフィルムを浸漬した後にフィルム表面の状態を観察して評価を行った。
評価項目1:25℃のイソプロパノール中に10分浸漬した後、風乾した。
評価項目2:25℃の2Nの塩酸溶液中に10分間浸漬した後、純水で洗浄して風乾燥した。
評価項目3:25℃の2Nの水酸化ナトリウム溶液中に浸漬した後、純水で洗浄して風乾した。
ポリイミド樹脂が変化無いものを〇、
ポリイミド樹脂が一部溶解しているものを△、
ポリイミド樹脂が完全に溶解しているもの×とした。
25μm厚みのポリイミドフィルム(株式会社カネカ製アピカル25NPI)表面にポリイミド樹脂溶液を最終フィルム厚みが25μmになるように塗布して、120℃で90分、160℃で30分乾燥してポリイミドフィルム積層体を得た。本ポリイミドフィルム積層体を30mm×10mmの短冊に切り出して、15mmのところで180°に10回折り曲げて塗膜を目視で確認してクラックの確認を行った。
○:硬化膜にクラックが無いもの
△:硬化膜に若干クラックがあるもの
×:硬化膜にクラックがあるもの。
上記の評価結果を表1に記載する。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン122gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
更に、ポリイミド前駆体組成物から得られる硬化被膜の特性を実施例1と同様の方法で行った。その評価結果を表1に記載する。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン140gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
更に、ポリイミド前駆体組成物から得られる硬化被膜の特性を実施例1と同様の方法で行った。その評価結果を表1に記載する。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン179gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名X-22-9409S、分子量1492、下記一般式(7)のシリコンジアミン、
更に、ポリイミド前駆体組成物から得られる硬化被膜の特性を実施例1と同様の方法で行った。その評価結果を表1に記載する。
4,4’―ジフェニルスルホンテトラカルボン酸二無水物40.0g(0.112mol)を1,2-ビス(2-メトキシエトキシ)エタン64.1gに分散し、20℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
更に、ポリイミド前駆体組成物から得られる硬化被膜の特性を実施例1と同様の方法で行った。その評価結果を表1に記載する。
4,4’―オキシジフタル酸二無水物20.0g(0.0645mol)を1,2-ビス(2-メトキシエトキシ)エタン32.1gに分散し、20℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
更に、ポリイミド前駆体組成物から得られる硬化被膜の特性を実施例1と同様の方法で行った。その評価結果を表1に記載する。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物300g(0.576mol)を1,2-ビス(2-メトキシエトキシ)エタン421gに分散し、80℃に保った。これにポリカーボネートジオールビス(4-アミノベンゾエート)(下記一般式(8)で表されるジアミンであり、
更に、ポリイミド前駆体組成物から得られる硬化被膜の特性を実施例1と同様の方法で行った。その評価結果を表1に記載する。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物300g(0.576mol)を1,2-ビス(2-メトキシエトキシ)エタン396gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
ポリイミドフィルム表面への塗膜の作製温度として120℃で90分、190℃で窒素雰囲気下で30分乾燥した以外は、実施例1と同様の方法で実験を実施し、評価を行った。その結果を表1に記載する。
ヘキサメチレンジアミン2.73g(23.5mmol)をジメチルアセトアミド24.0gに溶解し、これに3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物3.78g(11.75mmol)を30分間にわたり徐々に加え、ポリアミド結合を持ったオリゴマーを得た。1時間均一攪拌した後、3,3’,4,4’-ベンゾフェノンテトラカルボン酸3.02g(9.40mmol)を加え1時間撹拌を続けたところ、粘調な溶液が得られた(溶質濃度28重量%)。この溶液の粘度を測定したところ、3100ポイズであった。
実施例1と同様の方法で評価を行った。評価結果を表2に記載する。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン183gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
実施例1と同様の評価方法を行った結果を表2に記載する。
耐環境試験安定性が悪く、耐溶剤性、耐アルカリ性が悪いことが明らかになった。
4,4’-ジアミノジフェニルエーテル8.22g(41.1mmol)をN,N-ジメチルアセトアミド55.0gに溶解し、室温下で攪拌した。これにピロメリット酸二無水物11.9g(54.8mmol)を添加して、室温下で2時間攪拌した。メタノールを1.32g(41.1mmol)及びジメチルアミノエタノール0.066gを加えて、70℃湯浴上で2時間加熱攪拌した。室温まで冷却した後、4,4’-ジアミノジフェニルエーテル2.74g(13.7mmol)を加え、更に1時間攪拌を続けたところ、均一な溶液が得られた。この溶液の粘度は23℃で18ポイズであった。
溶液の貯蔵安定性を確認する為に、20℃に保った部屋の中で、10mlのスクリュー管で密封した状態で1ヶ月間放置し、1ヶ月後の粘度を測定した。そのときの粘度が23℃で50ポイズであり、室温での貯蔵安定性に問題があることが明らかになった。
実施例1と同様の評価方法を行った結果を表2に記載する。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン183gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
上記、イソシアネート系化合物を含まないイミド化したテトラカルボン酸を溶解した溶液を実施例1と同様の方法で評価を行った。その結果を表2に記載する。
ピロメリット酸二無水物 7.00g(32.1mmol)を1,2-ビス(2-メトキシエトキシ)エタン31.3gに分散して、水 2.31gを添加して、80℃で10時間攪拌して、ピロメリット酸溶液を得た。この溶液に、4,4-ジアミノジフェニルエーテル6.43g(32.1mmol)を添加して溶液を調製した。
この溶液を実施例1と同様の評価方法でフィルム化を試みたが、ポリイミドフィルム表面で固化してしまい、膜状にはならなかった。
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン183gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、下記一般式(7)のシリコンジアミン、
2,2-ビス[4-(3,4-ジカルボキシフェノキシ)フェニル]プロパン二無水物(以下BPADAと略す)200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン140gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、一般式(1)中のR1、R2がメチル基、n=3、m=6~11である。)を128g(0.154mol)投入し、30分間均一攪拌を行った。次いで、140℃に加熱して1時間均一攪拌を行い、次いで180℃に昇温させて3時間加熱還流を行いイミド化反応を行った。次いで、80℃まで冷却し水を27.7g(1.54mol)投入し、5時間加熱還流を行った。このようにしてイミド化したテトラカルボン酸(末端テトラカルボン酸シロキサンイミドオリゴマー)を溶解した溶液を得た。この溶液の固形分濃度は66重量%、溶液の粘度は23℃で140ポイズであった。この末端テトラカルボン酸溶液は、1ヶ月間室温で放置しておいても、粘度の変化は殆ど無く安定的な溶液であった。この合成した化合物を化合物Aと略す。
BPADA200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン159gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名X-22-9409S、分子量1492、式中R1、R2がメチル基もしくはフェニル基、n=3、m=9~12である。)を172g(0.115mol)投入し、30分間均一攪拌を行った。次いで、140℃に加熱して1時間均一攪拌を行い、次いで、180℃に昇温させて3時間加熱還流を行いイミド化反応を行った。次いで、80℃まで冷却し水を27.7g(1.54mol)投入し、5時間加熱還流を行った。このようにしてイミド化したテトラカルボン酸(末端テトラカルボン酸シロキサンイミドオリゴマー)を溶解した溶液を得た。この溶液の固形分濃度は67重量%、溶液の粘度は23℃で120ポイズであった。この末端テトラカルボン酸溶液は、1ヶ月間室温で放置しておいても、粘度の変化は殆ど無く安定的な溶液であった。この合成した化合物を化合物Bと略す。
BPADA200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン154gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名KF8010、分子量830、一般式(1)中のR1、R2がメチル基、n=3、m=6~11である。)を159g(0.192mol)投入し、30分間均一攪拌を行った。次いで、140℃に加熱して1時間均一攪拌を行い、180℃に昇温させて3時間加熱還流を行いイミド化反応を行った。80℃まで冷却し水を27.7g(1.54mol)投入し、5時間加熱還流を行った。このようにしてイミド化したテトラカルボン酸(末端テトラカルボン酸シロキサンイミドオリゴマー)を溶解した溶液を得た。この溶液の固形分濃度は66重量%、溶液の粘度は23℃で100ポイズであった。この末端テトラカルボン酸溶液は、1ヶ月間室温で放置しておいても、粘度の変化は殆ど無く安定的な溶液であった。この合成した化合物を化合物Cと略す。
BPADA200g(0.384mol)を1,2-ビス(2-メトキシエトキシ)エタン184gに分散し、80℃に保った。これにシリコンジアミン(シロキサンジアミン)(信越化学社製:商品名X-22-9409S、分子量1492、式中R1、R2がメチル基もしくはフェニル基、n=3、m=9~12である。)を229g(0.154mol)投入し、30分間均一攪拌を行った。次いで、140℃に加熱して1時間均一攪拌を行い、180℃に昇温させて3時間加熱還流を行いイミド化反応を行った。80℃まで冷却し水を27.7g(1.54mol)投入した。均一に30分間攪拌した後、80℃に加熱して5時間加熱還流を行った。このようにしてイミド化したテトラカルボン酸(末端テトラカルボン酸シロキサンイミドオリゴマー)を溶解した溶液を得た。この溶液の固形分濃度は67重量%、溶液の粘度は23℃で90ポイズであった。この末端テトラカルボン酸溶液は、1ヶ月間室温で放置しておいても、粘度の変化は殆ど無く安定的な溶液であった。この合成した化合物を化合物Dと略す。
合成例1で反応後に投入する水をメタノールに変更し、ハーフエステル化した。この合成した化合物を化合物Eと略す。
合成例1で反応後に水を投入することなく、上記反応を行い末端が無水物基のイミド化した酸無水物を得た。この合成した化合物を化合物Fと略す。
合成例1~4で得られた末端テトラカルボン酸(表3においては(A)成分と表す。)にイソシアネート系化合物(表3においては(B)成分と表す。)、感光性樹脂(表3においては(C)成分と表す。)、光重合開始剤(表3においては(D)成分と表す。)、有機溶剤を添加して感光性樹脂組成物溶液を作製した。それぞれの構成原料の樹脂固形分での配合量及び原料の種類を表3に記載する。なお、表中の溶媒である1,2-ビス(2-メトキシエトキシ)エタンは上記感光性樹脂組成物溶液等に含まれる溶剤等も含めた全溶剤量である。
評価結果を表4に示す。
上記感光性樹脂組成物溶液を、ベーカー式アプリケーターを用いて、75μmのポリイミドフィルム(株式会社カネカ製:商品名75NPI)に最終乾燥厚みが25μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分乾燥した。この乾燥フィルムは10枚用意した。9枚は50mm×50mmの面積が完全に透明な、ネガ型のフォトマスクをおいて、1枚には、ライン幅/スペース幅=100μm/100μmのネガ型フォトマスク(30mm長さ×100μm幅のラインが10本残るフォトマスク)を置いて窒素雰囲気下で紫外線を300mJ/cm2露光して感光させた。この感光フィルムに対し、1.0重量%の炭酸ナトリウム水溶液を30℃に加熱した溶液を用いて、1.0kgf/mm2の吐出圧で30秒間、スプレー現像を行った。現像後、純水で十分洗浄した後、170℃のオーブン中で60分加熱乾燥させて感光性樹脂組成物の硬化膜を作製した。
感光性樹脂組成物の感光性の評価は、上記(ポリイミドフィルム上への塗膜の作製)の項目で得られた硬化膜の表面観察を行い判定した。
ポリイミドフィルム表面に
〇:くっきりとしたライン幅/スペース幅=100/100μmの感光パターンが描けており、ライン部の剥離に伴うラインの揺れが発生しておらず、スペース部にも溶解残りが無いもの。
△:くっきりとしたライン幅/スペース幅=100/100μmの感光パターンが描けており、ライン部に剥離に伴うラインの揺れが発生しているが、スペース部には溶解残りが無いもの。
×:くっきりとしたライン幅/スペース幅=100/100μmの感光パターンが描けておらず、ライン部が剥離しており、しかも、スペース部には溶解残りが発生しているもの。
上記(ポリイミドフィルム上への塗膜の作製)の項目で得られた感光性樹脂組成物の硬化膜の接着強度をJIS K5400に従って碁盤目テープ法で評価した。
碁盤目テープ法で剥がれの無いものを○、
升目の95%以上が残存している場合を△、
升目の残存量が80%未満のものを×とした。
上記(ポリイミドフィルム上への塗膜の作製)の項目で得られた感光性樹脂組成物の硬化膜の耐溶剤性の評価を行った。評価方法は25℃のイソプロパノール中に15分間浸漬した後風乾し、フィルム表面の状態を観察した。
○:塗膜に異常がない。
×:塗膜に異常が発生する。
上記(ポリイミドフィルム上への塗膜の作製)の項目で得られた感光性樹脂組成物の硬化膜の耐酸性の評価を行った。評価方法は25℃の2N塩酸溶液中に15分間浸漬した後風乾し、フィルム表面の状態を観察した。
○:塗膜に異常(白化もしくは剥離)がないもの。
×:塗膜に異常(白化もしくは剥離)が発生する。
上記(ポリイミドフィルム上への塗膜の作製)の項目で得られた感光性樹脂組成物の硬化膜の耐アルカリ性の評価を行った。評価方法は25℃の2N水酸化ナトリウム溶液中に15分間浸漬した後風乾し、フィルム表面の状態を観察した。
○:塗膜に異常(白化もしくは剥離)がない。
×:塗膜に異常(白化もしくは剥離)が発生する。
上記(ポリイミドフィルム上への塗膜の作製)の項目と同様の方法で、25μm厚みのポリイミドフィルム(株式会社カネカ製アピカル25NPI)表面に感光性樹脂組成物の硬化膜積層フィルムを作製した。硬化膜積層フィルムを30mm×10mmの短冊に切り出して、15mmのところで180°に10回折り曲げて塗膜を目視で確認してクラックの確認を行った。
○:硬化膜にクラックが無いもの。
△:硬化膜に若干クラックがあるもの。
×:硬化膜にクラックがあるもの。
フレキシブル銅貼り積層版(銅箔の厚み12μm、ポリイミドフィルムは株式会社カネカ製アピカル25NPI、ポリイミド系接着剤で銅箔を接着している)上にライン幅/スペース幅=100μm/100μmの櫛形パターンを作製し、10容量%の硫酸水溶液中に1分間浸漬した後、純水で洗浄し銅箔の表面処理を行った。その後、ポリイミドフィルム上への硬化膜の作製方法と同様の方法で櫛形パターン上に感光性樹脂組成物の硬化膜を作製し試験片の調整を行った。85℃、85%RHの環境試験機中で試験片の両端子部分に100Vの直流電流を印加し、絶縁抵抗値の変化やマイグレーションの発生などを観察した。
○:試験開始後、500時間で10の6乗以上の抵抗値を示し、マイグレーション、デンドライトなどの発生が無いもの。
×:試験開始後、500時間でマイグレーション、デンドライトなどの発生があるもの。
上記実施例9の感光性樹脂組成物の固形分100重量部に対して、エポキシ樹脂(クレゾールノボラック型の多官能エポキシ樹脂であるエピクロンN―665)を5重量部投入した以外は、実施例9と同様の方法で評価を行った。更に、半田耐熱性の試験として、下記評価方法で評価を行った。評価結果を表4に示す。
感光性樹脂組成物溶液を、ベーカー式アプリケーターを用いて、75μmのポリイミドフィルム(株式会社カネカ製:商品名75NPI)に最終乾燥厚みが25μmになるように100mm×100mmの面積に流延・塗布し、80℃で20分乾燥した後、50mm×50mmの面積が完全に透明なネガ型フォトマスクを置いて窒素雰囲気下で紫外線を300mJ/cm2露光して感光させた。この感光フィルムに対し、1.0重量%の炭酸ナトリウム水溶液を30℃に加熱した溶液を用いて、1.0kgf/mm2の吐出圧で30秒間、スプレー現像を行った。現像後、純粋で十分洗浄した後、170℃のオーブン中で60分加熱乾燥させて感光性樹脂組成物の硬化膜を作製した。
上記塗工膜を260℃で完全に溶解してある半田浴に感光性樹脂組成物の硬化膜が塗工してある面が接する様に浮かべて10秒後に引き上げた。その操作を3回行い、硬化膜の接着強度をJIS K5400に従って碁盤目テープ法で評価した。
碁盤目テープ法で剥がれの無いものを○、
升目の95%以上が残存している場合を△、
升目の残存量が80%未満のものを×とした。
上記実施例10の感光性樹脂組成物の固形分100重量部に対して、エポキシ樹脂(クレゾールノボラック型の多官能エポキシ樹脂であるエピクロンN―665)を5重量部投入した以外は、実施例9と同様の方法で評価を行った。更に、半田耐熱性の試験として、実施例13と同様の評価方法で評価を行った。評価結果を表4に示す。
合成例5で得られたハーフエステル化した化合物を用いた以外は実施例9と同様の方法で感光性樹脂組成物溶液を作製し、実施例9と同様の方法で評価を行った。評価結果を表5に示す。イミド化が充分には進んでおらず、耐湿絶縁性の非常に悪いものになった。
合成例6で合成した化合物は、末端が無水物基のイミドシロキサンオリゴマーが、ジアミノ化合物と反応し、高粘度の溶液となった。評価の際には、使用可能な粘度範囲にまで1,2-ビス(2-メトキシエトキシ)エタンを添加して溶液の粘度を低下させた。評価結果を表5に示す。感光性が悪いものになった。
※2 三井化学ポリウレタン社製:商品名タケネート B-815N、水添ジフェニルメタンジイソシアネート系ブロックイソシアネート、固形分:60%、NCO含有量:7.3%
※3 東亜合成社製 製品名M-5710(2-ヒドロキシ-3-フェノキシプロピルアクリレート)
※4 新中村化学社製 ビスフェノールA EO変性ジアクリレート 分子量が1684
※5 チバ・スペシャルティーケミカルズ社製 光重合開始剤
Claims (15)
- 請求項1~5のいずれか1項に記載のポリイミド前駆体組成物を40~90重量%の溶質濃度に溶解して得られるポリイミド前駆体組成物溶液。
- 請求項1~5のいずれか1項に記載のポリイミド前駆体組成物または請求項6に記載のポリイミド前駆体組成物溶液から得られるポリイミド塗膜。
- 請求項1~5のいずれか1項に記載のポリイミド前駆体組成物または請求項6に記載のポリイミド前駆体組成物溶液をプリント配線板に塗工し、加熱してイミド化して得られるポリイミド塗膜付きプリント配線板。
- 請求項1~5のいずれか1項に記載のポリイミド前駆体組成物と、少なくとも感光性樹脂、及び、光重合開始剤を含有することを特徴とする感光性樹脂組成物。
- 下記一般式(3)
に示すテトラカルボン酸二無水物と、
下記一般式(4)
に示すジアミンとを、
一般式(3)に示すテトラカルボン酸二無水物1モルに対して一般式(4)に示すジアミン0.20~0.80モルの比率で反応を行いアミド酸を得る工程、
前記アミド酸をイミド化し、イミドを得る工程、及び
前記イミドに水を反応させて、内部がイミド化しており、末端がテトラカルボン酸である、イミド化したテトラカルボン酸を得る工程を含み、
さらに、前記工程で得たイミド化したテトラカルボン酸と、イソシアネート系化合物とを、イミド化したテトラカルボン酸1モルに対して、イソシアネート系化合物を、前記アミド酸を得る工程で用いた一般式(4)に示すジアミンとあわせた合計の比率が、0.70モル~1.30モルとなる比率で、混合する工程を含むことを特徴とする、ポリイミド前駆体組成物の製造方法。 - 請求項10または11で得られるポリイミド前駆体組成物を40~90重量%の溶質濃度になるように有機溶剤中に溶解する工程を含むことを特徴とするポリイミド前駆体組成物溶液の製造方法。
- 請求項10または11で得られるポリイミド前駆体組成物または請求項12で得られるポリイミド前駆体組成物溶液からポリイミド塗膜を得る工程を含むことを特徴とする、ポリイミド塗膜の製造方法。
- 請求項10または11で得られるポリイミド前駆体組成物または請求項12で得られるポリイミド前駆体組成物溶液をプリント配線板に塗工し、加熱してイミド化する工程を含むことを特徴とするポリイミド塗膜付きプリント配線板の製造方法。
- 請求項10または11で得られるポリイミド前駆体組成物と、少なくとも感光性樹脂、及び、光重合開始剤を混合する工程を含むことを特徴とする感光性樹脂組成物の製造方法。
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JP2014130344A (ja) * | 2012-11-30 | 2014-07-10 | Fujifilm Corp | 硬化性樹脂組成物、これを用いたイメージセンサチップの製造方法及びイメージセンサチップ |
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US20110061914A1 (en) | 2011-03-17 |
CN102037043A (zh) | 2011-04-27 |
KR20110008090A (ko) | 2011-01-25 |
JP5469062B2 (ja) | 2014-04-09 |
US8729402B2 (en) | 2014-05-20 |
JPWO2009145065A1 (ja) | 2011-10-06 |
KR101597146B1 (ko) | 2016-02-24 |
CN102037043B (zh) | 2013-11-20 |
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