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WO2020150913A1 - 感光性聚酰亚胺树脂组合物及其聚酰亚胺膜 - Google Patents

感光性聚酰亚胺树脂组合物及其聚酰亚胺膜 Download PDF

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Publication number
WO2020150913A1
WO2020150913A1 PCT/CN2019/072780 CN2019072780W WO2020150913A1 WO 2020150913 A1 WO2020150913 A1 WO 2020150913A1 CN 2019072780 W CN2019072780 W CN 2019072780W WO 2020150913 A1 WO2020150913 A1 WO 2020150913A1
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WIPO (PCT)
Prior art keywords
bis
resin composition
dianhydride
trimellitic anhydride
polyimide film
Prior art date
Application number
PCT/CN2019/072780
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English (en)
French (fr)
Inventor
黄堂杰
庄朝钦
史谕樵
谢坤翰
Original Assignee
律胜科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 律胜科技股份有限公司 filed Critical 律胜科技股份有限公司
Priority to PCT/CN2019/072780 priority Critical patent/WO2020150913A1/zh
Priority to US16/970,534 priority patent/US20210088903A1/en
Priority to CN201980001571.8A priority patent/CN110476123B/zh
Publication of WO2020150913A1 publication Critical patent/WO2020150913A1/zh

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0047Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00Characterised 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
    • C08J2379/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general

Definitions

  • the present invention relates to a photosensitive resin composition, and in particular to a photosensitive resin composition containing photosensitive polyimide as a main component.
  • polyimide resin is prepared by polycondensation of aromatic tetracarboxylic acid or its derivatives, aromatic diamine and aromatic diisocyanate.
  • the prepared polyimide resin has excellent heat resistance and chemical resistance. It is widely used in electronic materials such as semiconductor encapsulants because of its performance, mechanical and electrical properties.
  • Polyimide is used in the manufacturing process of semiconductor devices, and it is often necessary to use Micro Lithography to make circuit patterns. If traditional polyimide is used, an additional layer of photoresist must be added to Perform etching. Therefore, the photosensitive polyimide (PSPI) has the characteristics of both photoresist and insulating protection material, which can simplify the manufacturing process, making the manufacturing process of flexible electronic materials have considerable progress, and is currently a very popular cutting-edge material.
  • PSPI photosensitive polyimide
  • insulating films with good shielding properties are required.
  • one of the known methods is to coat a white resin (such as epoxy or acrylic resin) on the polyimide film to form a dual-layered composite Polyimide film.
  • a white resin such as epoxy or acrylic resin
  • the additional coating resin usually increases the production cost and reduces the yield. Therefore, there is a need for a more cost-effective polyimide film.
  • the object of the present invention is to provide a more cost-effective polyimide film.
  • the photosensitive polyimide resin composition comprises: (a) photosensitive polyimide, which is represented by formula (1); (b) titanium dioxide, whose particle size is 0.2 Micron-10 microns; (c) photo radical initiator; (d) radical polymerizable compound; (e) solvent, which is used to dissolve the photosensitive polyimide,
  • X is derived from tetracarboxylic dianhydride
  • Y is derived from diamine
  • m is a positive integer from 1 to 5000.
  • the tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4 , 4'-oxydiphthalic anhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 -Bis(3,4-dicarboxyphenyl)propane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy) Group) phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl] Propane dianhydride, ethylene glyco
  • the diamine is 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-methylenediphenylamine, 4,4'-methylenediphenylsulfone Aniline, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2′-bis(trifluoromethyl)benzidine, 2,2 '-Dimethylbenzidine, 3,3'-Dihydroxybenzidine, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1, 4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , 2,2-bis[4-(4-aminophenoxy
  • the particle size of the titanium dioxide is 0.3 ⁇ m to 5 ⁇ m.
  • the titanium dioxide accounts for 30-70% of the total solid content of the photosensitive polyimide resin composition. More preferably, the titanium dioxide accounts for 35-50% of the total solid content of the photosensitive polyimide resin composition.
  • the radically polymerizable compound is a compound having at least two (meth)acrylate groups.
  • the radically polymerizable compound is a polyamic acid ester having a (meth)acrylate group. More preferably, the content of the polyamic acid ester having a (meth)acrylate group in the radical polymerizable compound is 10% by weight to 98% by weight.
  • the polyimide film formed by the resin composition has a reflectance of 85% or more at a wavelength of 450 nm.
  • the color difference ⁇ E*ab of the polyimide film formed by the resin composition before and after reflow at 260° C. is 2 or less.
  • the color difference ⁇ E*ab of the polyimide film formed by the resin composition before and after baking at 200° C. for 2 hours is 2 or less.
  • the hardness of the polyimide film formed by the resin composition is 7H or more.
  • the polyimide film formed from the resin composition has a hole pattern with a hole diameter of 100 ⁇ m or less.
  • the present invention also provides a polyimide film formed from the aforementioned resin composition.
  • the color difference ⁇ E*ab of the polyimide film before and after reflow at 260° C. is 2 or less.
  • the color difference ⁇ E*ab of the polyimide film before and after baking at 200°C for 2 hours is 2 or less.
  • the hardness of the polyimide film is 7H or more.
  • the polyimide film has a hole pattern with a pore diameter of 100 ⁇ m or less.
  • the present invention also provides a substrate comprising the aforementioned polyimide film.
  • the photosensitive polyimide resin composition of the present invention is composed of a combination of specific components, and by adding titanium dioxide with a particle diameter of 0.2 to 10 microns, the formed polyimide film can have low yellowness and High reflectivity characteristics.
  • the present invention provides a photosensitive polyimide resin composition
  • a photosensitive polyimide resin composition comprising: (a) photosensitive polyimide, which is represented by formula (1); (b) titanium dioxide, whose particle size is 0.2 micrometers to 10 Micron; (c) photo radical initiator; (d) radical polymerizable compound; (e) solvent, which is used to dissolve the photosensitive polyimide,
  • X is derived from tetracarboxylic dianhydride
  • Y is derived from diamine
  • m is a positive integer from 1 to 5000, such as: 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500. In some embodiments, m is between any two of the foregoing values.
  • the photosensitive polyimide of the present invention is a solvent-soluble polyimide that undergoes chemical ring closure or thermal ring closure by reacting diamine and tetracarboxylic dianhydride.
  • the diamine and tetracarboxylic dianhydride are usually dissolved in an organic solvent, and the resulting solution is placed under controlled temperature conditions under stirring until the polymerization of the tetracarboxylic dianhydride and the diamine is completed to obtain poly Imide precursor (ie polyamic acid).
  • the concentration of the polyamic acid solution thus obtained is usually 5 wt% to 35 wt%, preferably 10 wt% to 30 wt%.
  • the concentration is within this range, an appropriate molecular weight and solution viscosity can be obtained.
  • the polymerization method of the polyimide is not particularly limited, and the order of addition of the tetracarboxylic dianhydride monomer and the diamine monomer, the combination of monomers, and the amount of addition thereof are also not particularly limited.
  • the polyimide of the present invention is a random polymerization or sequential polymerization that can produce block components by a known polymerization method.
  • the preparation method of the polyimide precursor (polyamic acid) to form a polyimide by ring closure is not particularly limited. More specifically, a chemical ring-closure method can be used, that is, under nitrogen or oxygen, pyridine, triethylamine or N,N-diisopropylethylamine, etc., which are not limited as alkaline reagents, and as dehydration
  • a chemical ring-closure method can be used, that is, under nitrogen or oxygen, pyridine, triethylamine or N,N-diisopropylethylamine, etc., which are not limited as alkaline reagents, and as dehydration
  • the acetic anhydride of the reagent is added to the polyamic acid. After the reaction is completed, the colloid is washed and filtered with water to obtain polyimide powder.
  • the closed loop method of heating can also be used.
  • the polyamic acid is added to the azeotropic reagent, not limited to toluene or xylene, and the temperature is increased to 180 degrees to remove the water and the azeotropic reagent generated by the loop closure of the polyamic acid.
  • azeotropic reagent not limited to toluene or xylene
  • solvent-soluble polyimide In the process of preparing the solvent-soluble polyimide, other reagents to improve the reaction efficiency can be added, such as but not limited to: catalysts, inhibitors, azeotropic agents, leveling agents, or a combination of these reagents.
  • the photosensitive polyimide of the present invention is obtained by the polymerization reaction of tetracarboxylic dianhydride and diamine. That is, in the present invention, X is a tetravalent organic group derived from tetracarboxylic dianhydride, and Y is a divalent organic group derived from diamine.
  • tetracarboxylic dianhydride examples include, but are not limited to: 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride , 4,4'-oxydiphthalic anhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2 , 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyl) Phenoxy)phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)benzene Base) propane dianhydride, ethylene glycol
  • diamines examples include, but are not limited to: 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-methylenediphenylamine, 4,4'-methylene Diphenylamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2′-bis(trifluoromethyl)benzidine, 2 , 2'-dimethylbenzidine, 3,3'-dihydroxybenzidine, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl ]Propane, 2,2-bis[4-(4
  • the titanium dioxide preferably accounts for 30 to 70% of the total solid content of the photosensitive polyimide resin composition, more preferably 35 to 50%.
  • the photo-radical initiator is a commonly used initiator in photosensitive resin compositions.
  • photo-radical initiators may include, but are not limited to: oxime compounds such as oxime derivatives, ketone compounds (including acetophenones, benzophenones, and thioxanthones), triazine compounds, and benzoin Compound, metallocene compound, triazine compound or acyl phosphine compound. These initiators can be used alone or in combination of two or more (such as three, four, and five). From the viewpoint of exposure sensitivity, the photoradical initiator is preferably an acylphosphine compound or an oxime compound.
  • oxime compounds such as oxime derivatives may include, but are not limited to: O-acyl oxime-based compounds, 2-(ortho-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2- Octanedione, 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxy Carbonyl- ⁇ -oxyamino-1-phenylpropan-1-one and the like. These compounds can be used alone or in combination of two or more (such as three, four, and five).
  • O-acyl oxime-based compounds may include, but are not limited to: 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4 -Yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1- (4-Phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1 -Oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-oxime-O-acetate, etc.
  • O-acyl oxime-based compounds can be used alone or in combination of two or more (such as three, four, and five).
  • acylphosphine compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, but are not limited to this. These acylphosphine compounds may be used alone or in combination of two or more kinds.
  • the content of the photoradical initiator is preferably 0.1% to 30% by weight of the main resin, more preferably 1% to 20% by weight.
  • the content of the photo-radical initiator is within the range, the polyimide is fully cured during exposure during the pattern formation process, which can ensure that the polyimide film has excellent reliability and the pattern has excellent resolution Heat resistance, light resistance and chemical resistance in close contact.
  • the photo-radical initiator can be used together with a photosensitizer, which can cause a chemical reaction by absorbing light and being excited, and then transfer its energy.
  • photosensitizers may include, but are not limited to: tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol tetraalkyl-3-mercaptopropionate, and the like. These photosensitizers can be used alone or in combination of two or more (such as three).
  • the radically polymerizable compound is a photoradical crosslinking agent, and its kind is not particularly limited.
  • the radically polymerizable compound is a compound having at least two (meth)acrylate groups, such as: a compound having two (meth)acrylate groups, a compound having three A compound having a (meth)acrylate group, a compound having four (meth)acrylate groups, a compound having five (meth)acrylate groups, or a compound having six (meth)acrylate groups.
  • the polyamic acid ester having a (meth)acrylate group is obtained by reacting tetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and diamine.
  • the amount of the radical polymerizable compound The content is preferably 1% by mass to 50% by mass.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 40% by mass or less.
  • One kind of radical polymerizable compound can be used alone, or two or more kinds (such as two, three, four) can be used in combination, preferably three kinds of radical polymerizable compounds are mixed for use, more preferably three At least one of the species is a polyamic acid ester having a (meth)acrylate group.
  • the content of the polyamic acid ester having a (meth)acrylate group in the radically polymerizable compound is preferably 10% by weight to 98% by weight, more preferably 30% by weight to 95% by weight, Particularly preferably, it is 50% by weight to 90% by weight. If the content of the polyamic acid ester having a (meth)acrylate group is within the above range, a cured film with more excellent curability and heat resistance can be formed. Only one type of radical polymerizable compound may be used, and two or more types may be used. When two or more are used, it is preferable that the total amount falls within the aforementioned range.
  • the crosslinking bond generated by the radical reaction initiated by the photoradical initiator and UV radiation irradiation can improve the pattern forming ability.
  • exposure and curing can sufficiently occur during pattern formation, and the contrast of the alkaline developer can be improved.
  • the solvent is not particularly limited as long as it can dissolve the photosensitive polyimide.
  • the solvent include, but are not limited to: ethyl acetate, n-butyl acetate, ⁇ -butyrolactone, ⁇ -caprolactone, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol Alcohol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol mono Propyl ether acetate, methyl ethyl ketone, cyclohexanone, cyclopentanone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide or N,N-dimethylace
  • solvents can be used alone or in combination of two or more (such as two, three or four). From the viewpoint of improving the coating surface state, it is preferable to mix two or more solvents.
  • the content of the solvent is preferably 5 mass% to 80 mass% of the total solid content of the photosensitive resin composition, more preferably 5 mass% to 70% by mass, particularly preferably 10% by mass to 60% by mass.
  • the photosensitive polyimide resin composition of the present invention may or may not add additives.
  • the choice of the additive depends on the application of the photosensitive polyimide resin composition of the present invention.
  • the additives include, but are not limited to: higher fatty acid derivatives, surfactants, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, anti-agglomeration agents, leveling agents, or two or more of these additives The combination. When blending these additives, it is preferable to set the total blending amount to 10% by mass or less of the solid content of the photosensitive resin composition.
  • the present invention also provides a polyimide film formed from the aforementioned resin composition.
  • the color difference ⁇ E*ab of the polyimide film before and after reflow at 260° C. is 2 or less.
  • the color difference ⁇ E*ab of the polyimide film before and after baking at 200° C. for 2 hours is 2 or less.
  • the hardness of the polyimide film is 7H or more.
  • the polyimide film has a hole pattern with a pore diameter of 100 ⁇ m or less.
  • the photosensitive polyimide resin composition can be coated on a substrate by a coating method such as spin coating or cast coating, and then prebaked (prebake ) The solvent is removed to form a pre-baked coating film.
  • prebake prebaked
  • the pre-bake conditions vary depending on the types and mixing ratios of the ingredients, and usually the temperature is between 80 and 120°C for 5 to 15 minutes.
  • the coating film is exposed under a mask.
  • the light used for the exposure is preferably ultraviolet rays such as g-line, h-line, and i-line.
  • the ultraviolet irradiation device can be (ultra) high pressure mercury lamp and metal halide light.
  • the developer include, but are not limited to: methanol, ethanol, propanol, isopropanol, butanol, ethyl acetate, n-butyl acetate, ⁇ -butyrolactone, ⁇ -caprolactone, diethylene glycol two Methyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ethyl ketone, cyclohexanone
  • the developer composed of the above organic solvent When used, it is usually washed with an organic solvent after development, and then dried with compressed air or compressed nitrogen. Then, a post-bake treatment is performed using a heating device such as a hot plate or an oven, and the temperature of the post-bake treatment is usually 180 to 250°C. After the above processing steps, a protective film can be formed.
  • the present invention also provides a substrate comprising the aforementioned polyimide film.
  • TFMB 2,2'-bis(trifluoromethyl)benzidine
  • DMAc 1,3-bis(trifluoromethyl)benzidine
  • TMPG propylene glycol bis(trimellitic anhydride)
  • the polyimide was precipitated in 5 liters of water, and the mixture of water and polyimide was stirred for 15 minutes at a speed of 5000 rpm.
  • the polyimide was collected by filtration, and it was poured into 4 liters of water again, and further stirred for 30 minutes, and filtered again.
  • the obtained polyimide was dried at 45° C. under reduced pressure for 3 days to obtain a dried polyimide (TMPG-TFMB PI(A1)).
  • the result of 1 H-NMR measurement of the obtained A1 is shown below (the ratio of the hydrogen number is defined by the structural unit that is not repeated).
  • TMPG Trimellitic anhydride
  • TFMB 2,2'-bis(trifluoromethyl)benzidine
  • HEMA 2-hydroxyethyl methacrylate
  • reaction mixture was cooled to -10°C, while maintaining the temperature at -10°C ⁇ 4°C, 11.9 g (100.0 mmol) of thionyl chloride was added over 10 minutes. During the addition of thionyl chloride, the viscosity increased. After diluting with 50 mL of dimethylacetamide, the reaction mixture was stirred at room temperature for 2 hours.
  • the polyamic acid ester having a methacrylate group was collected by filtration, and it was poured into 4 liters of water again, and further stirred for 30 minutes and filtered again. Then, under reduced pressure, the obtained polyamic acid ester having a methacrylate group was dried at 45°C for 3 days to obtain a dried polyamic acid ester having a methacrylate group (HEMA-TMPG- TFMB PAE(D3)).
  • the result of 1 H-NMR measurement of the obtained D3 is shown below (the ratio of the hydrogen number is defined by the structural unit that is not repeated).
  • Example 1-6 and Comparative Example 1-4 Preparation of photosensitive polyimide resin composition
  • the components used in the photosensitive polyimide resin composition are as follows. The components described below were mixed with a solvent in the weight ratio shown in Table 1 to prepare a solution with a solid content of 30%, which is a coating liquid of the photosensitive polyimide resin composition.
  • Component A1 TMPG-TFMB PI
  • Component B1 TiO2 with a particle size of 0.4 ⁇ m
  • Component B2 TiO2 with a particle size of 5.0 ⁇ m
  • Component B3 TiO2 with a particle size of 10.0 ⁇ m
  • Component B4 TiO2 with a particle size of 0.1 ⁇ m
  • Component B5 TiO2 with a particle size of 12.0 ⁇ m
  • the photosensitive resin composition is coated on a copper foil substrate, and the film is dried at 90 degrees for 5 minutes. After exposure through a photomask, the exposed photosensitive polyimide resin composition layer is treated with cyclopentanone. Development in 60 seconds.
  • the following criteria are used to evaluate whether the formed pattern has a line width with good edge sharpness. The smaller the line width of the photosensitive polyimide resin composition layer is, the larger the difference in solubility between the light-irradiated part and the non-light-irradiated part with respect to the developer becomes, and it is a better result. In addition, the smaller the change in line width with respect to the change in exposure energy, the wider the exposure latitude, which becomes a better result.
  • the b value in the color system (L, a, b) was measured using a spectrophotometer CM-600d (manufactured by Konica Minolta Sensing).
  • CM-600d manufactured by Konica Minolta Sensing
  • CM-600d manufactured by Konica Minolta Sensing
  • the polyimide film prepared in the embodiment and the comparative example of the present invention is white due to the addition of titanium dioxide as a white pigment, and has shielding properties. As shown in Table 1, the polyimide film formed from the photosensitive polyimide resin composition of the present invention has excellent performance in terms of yellowness, reflectance, hardness, and heat resistance.
  • the protective film formed can simultaneously have high reflectivity and low heat yellowing; and the hardening
  • the film can be applied to substrates contained in carrier-like substrates, liquid crystal displays, organic electroluminescent displays, semiconductor elements, or printed circuit boards.

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Abstract

一种感光性聚酰亚胺树脂组合物,其包含:(a)感光性聚酰亚胺,其由式(1)所表示;(b)二氧化钛,其粒径为0.2微米~10微米;(c)光自由基引发剂;(d)自由基聚合性化合物;(e)溶剂,其用于溶解该感光性聚酰亚胺,其中,X来源于四羧酸二酐,Y来源于二胺,m为1~5000中的正整数。

Description

感光性聚酰亚胺树脂组合物及其聚酰亚胺膜 技术领域
本发明涉及一种感光性树脂组合物,特别涉及一种以感光性聚酰亚胺为主成分的感光性树脂组合物。
背景技术
一般来说,聚酰亚胺树脂是由芳香族的四羧酸或其衍生物与芳香二胺、芳香二异氰酸酯缩聚而制备,制备所得的聚酰亚胺树脂具有优良的耐热性、耐化学性、机械和电特性,因而被广泛用于如半导体密封剂等电子材料。
聚酰亚胺应用于半导体元件的制程中,往往需要利用微影成像技术(Micro Lithography)来制作线路图形,如果使用传统的聚酰亚胺,则必须额外加入一层光阻材料(photoresist)以进行蚀刻。因此,感光性聚酰亚胺(Photosensitive polyimide,PSPI)由于同时具有光阻及绝缘保护材料的特性,可以简化制程,使得软板电子材料制程有相当的进步,为目前相当热门的尖端材料。
然而,在某些设计需求上,会需要具备良好遮蔽性的绝缘薄膜。为了获得具备良好遮蔽性的聚酰亚胺薄膜,已知方式之一是在聚酰亚胺薄膜上涂布白色树脂(例如环氧树脂或丙烯酸系树脂)以形成双层(dual-layered)复合聚酰亚胺薄膜。然而,该方法虽可使聚酰亚胺薄膜呈现白色而具有遮蔽性,但额外涂布的树脂通常会增加制作成本、降低良率。因此,需有一种更具成本效益的聚酰亚胺膜。
发明内容
有鉴于此,本发明的目的是提供一种更具成本效益的聚酰亚胺膜。
为达上述目的,本发明所提供的感光性聚酰亚胺树脂组合物包 含:(a)感光性聚酰亚胺,其由式(1)所表示;(b)二氧化钛,其粒径为0.2微米~10微米;(c)光自由基引发剂;(d)自由基聚合性化合物;(e)溶剂,其用于溶解该感光性聚酰亚胺,
Figure PCTCN2019072780-appb-000001
其中,X来源于四羧酸二酐,Y来源于二胺,m为1~5000中的正整数。
较佳地,该四羧酸二酐为3,3′,4,4′-联苯四羧酸二酐、3,3′,4,4′-二苯甲酮四羧酸二酐、4,4′-氧联二邻苯二甲酸酐、双(3,4-二羧基苯基)甲烷二酐、2,2-二(3,4-二羧基苯基)丙烷二酐、2,2-双(3,4-二羧基苯基)丙烷二酐、1,3-双(3,4-二羧基苯氧基)苯二酐、1,4-双(3,4-二羧基苯氧基)苯二酐、4,4′-双(3,4-二羧基苯氧基)联苯二酐、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐、乙二醇双(偏苯三酸酐)(TMEG)、丙二醇双(偏苯三酸酐)(TMPG)、1,2-丙二醇双(偏苯三酸酐)、丁二醇双(偏苯三酸酐)、2-甲基-1,3-丙二醇双(偏苯三酸酐)、二丙二醇双(偏苯三酸酐),2-甲基-2,4-戊二醇双(偏苯三酸酐)、二甘醇双(偏苯三酸酐)、四甘醇双(偏苯三酸酐)、六甘醇双(偏苯三酸酐)、新戊二醇双(偏苯三酸酐)、对苯二酚双(2-羟乙基)醚双(偏苯三酸酐)、2-苯基-5-(2,4-二甲苯基)-1,4-氢化醌双(偏苯三酸酐)、2,3-二氰基氢醌环丁烷-1,2,3,4-四羧酸二酐、1,2,3,4-环戊烷四羧酸二酐、1,2,4,5-环己烷四羧酸二酐、双环[2.2.1]庚烷-2,3,5,6-四羧酸二酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、双环[2.2.2]辛烷-2,3,5,6-四羧酸二酐、2,3,5-三羧基-环戊基乙酸二酐、双环[2.2.1]庚烷-2,3,5-三羧基-6-乙酸二酐、十氢-1,4,5,8-二甲醇萘-2,3,6,7-四羧酸二酐、丁-1,2,3,4-四羧酸二酐、3,3′,4,4′-二环己基四羧酸二酐或前述四羧酸二酐任意二种以上的组合。
较佳地,该二胺为3,3′-二氨基二苯砜、4,4′-二氨基二苯砜、3,3′-亚甲基二苯胺、4,4′-亚甲基二苯胺、2,2-双(4-氨基苯基)丙烷、2,2-双 (4-氨基苯基)六氟丙烷、2,2′-双(三氟甲基)联苯胺、2,2′-二甲基联苯胺、3,3′-二羟基联苯胺、1,3-双(3-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、4,4′-双(4-氨基苯氧基)联苯、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,3-双[4-(3-氨基苯氧基)苯甲酰基]苯、4,4′-二氨基苯甲酰苯胺、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、5-氨基-2-(对氨基苯基)苯并噁唑、6-氨基-2-(对氨基苯基)苯并噁唑或前述二胺任意二种以上的组合。
较佳地,该二氧化钛的粒径为0.3微米~5微米。
较佳地,该二氧化钛占该感光性聚酰亚胺树脂组合物的固体成分总重的30~70%。更佳地,该二氧化钛占该感光性聚酰亚胺树脂组合物的固体成分总重的35~50%。
较佳地,该自由基聚合性化合物为具有至少二个(甲基)丙烯酸酯基的化合物。
较佳地,该自由基聚合性化合物为具有(甲基)丙烯酸酯基的聚酰胺酸酯。更佳地,该具有(甲基)丙烯酸酯基的聚酰胺酸酯在自由基聚合性化合物中的含量为10重量%~98重量%。
较佳地,该树脂组合物所形成的聚酰亚胺膜在波长450nm下的反射率为85%以上。
较佳地,该树脂组合物所形成的聚酰亚胺膜的经260℃回焊前后的色差ΔE*ab为2以下。
较佳地,该树脂组合物所形成的聚酰亚胺膜的经200℃烘烤2小时前后的色差ΔE*ab为2以下。
较佳地,该树脂组合物所形成的聚酰亚胺膜的硬度为7H以上。
较佳地,该树脂组合物所形成的聚酰亚胺膜具有孔径为100μm以下的孔图案。
本发明还提供一种聚酰亚胺膜,其由前述树脂组合物所形成。
较佳地,该聚酰亚胺膜经260℃回焊前后的色差ΔE*ab为2以下。
较佳地,该聚酰亚胺膜经200℃烘烤2小时前后的色差ΔE*ab为 2以下。
较佳地,该聚酰亚胺膜的硬度为7H以上。
较佳地,该聚酰亚胺膜具有孔径为100μm以下的孔图案。
本发明还提供一种基板,其包含前述聚酰亚胺膜。
本发明的感光性聚酰亚胺树脂组合物由特定成分组合而成,并且其通过添加粒径为0.2微米~10微米的二氧化钛,而能使所形成的聚酰亚胺膜具有低黄度及高反射率的特性。
具体实施方式
本发明提供一种感光性聚酰亚胺树脂组合物,其包含:(a)感光性聚酰亚胺,其由式(1)所表示;(b)二氧化钛,其粒径为0.2微米~10微米;(c)光自由基引发剂;(d)自由基聚合性化合物;(e)溶剂,其用于溶解该感光性聚酰亚胺,
Figure PCTCN2019072780-appb-000002
其中,X来源于四羧酸二酐,Y来源于二胺,m为1~5000中的正整数,诸如:500、1000、1500、2000、2500、3000、3500、4000、4500。在一些实施方式中,m介于前述任两个数值之间。
本发明的感光性聚酰亚胺为通过二胺和四羧酸二酐反应,经化学闭环或热闭环的溶剂可溶型聚酰亚胺。具体而言,通常是将二胺和四羧酸二酐溶解在有机溶剂中,并且在搅拌下将所得溶液置于受控温度条件下直至四羧酸二酐与二胺的聚合完成,得到聚酰亚胺前驱体(即聚酰胺酸)。由此得到的聚酰胺酸的溶液的浓度通常为5重量%至35重量%,较佳是10重量%至30重量%。当浓度在该范围内时,可获得适当的分子量和溶液粘度。在本发明中,该聚酰亚胺的聚合方法并无特别限制,且四羧酸二酐单体及二胺单体的添加顺序、单体的组合、及其添加量也无特别限制。例如,本发明的聚酰 亚胺是可通过已知的聚合方法而产生嵌段组分的无规聚合或序列聚合。
该聚酰亚胺前驱体(聚酰胺酸)闭环成聚酰亚胺的制备方法并无特别的限制。更具体地,可使用化学方式的闭环方法,即在氮气或氧气下,将不限定的作为碱性试剂的吡啶、三乙胺或N,N-二异丙基乙基胺等、及作为脱水试剂的醋酸酐加入聚酰胺酸中,反应结束后,胶体经由水洗过滤,即可得到聚酰亚胺粉末。另外,也可使用加热方式的闭环方法,将聚酰胺酸加入共沸试剂,不限定甲苯或二甲苯等,升温至180度,将聚酰胺酸闭环产生的水及共沸试剂去除,反应结束后,即可制得溶剂可溶型聚酰亚胺。制备溶剂可溶型聚酰亚胺过程中,可添加增进反应效率的其他试剂,例如但不限于:催化剂、抑制剂、共沸剂、流平剂或这些试剂的组合。
本发明的感光性聚酰亚胺由四羧酸二酐与二胺进行聚合反应而得。也就是说,在本发明中,X是衍生自四羧酸二酐的四价有机基团,Y是衍生自二胺的二价有机基团。
该四羧酸二酐的实例包括但不限于:3,3′,4,4′-联苯四羧酸二酐、3,3′,4,4′-二苯甲酮四羧酸二酐、4,4′-氧联二邻苯二甲酸酐、双(3,4-二羧基苯基)甲烷二酐、2,2-二(3,4-二羧基苯基)丙烷二酐、2,2-双(3,4-二羧基苯基)丙烷二酐、1,3-双(3,4-二羧基苯氧基)苯二酐、1,4-双(3,4-二羧基苯氧基)苯二酐、4,4′-双(3,4-二羧基苯氧基)联苯二酐、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐、乙二醇双(偏苯三酸酐)(TMEG)、丙二醇双(偏苯三酸酐)(TMPG)、1,2-丙二醇双(偏苯三酸酐)、丁二醇双(偏苯三酸酐)、2-甲基-1,3-丙二醇双(偏苯三酸酐)、二丙二醇双(偏苯三酸酐),2-甲基-2,4-戊二醇双(偏苯三酸酐)、二甘醇双(偏苯三酸酐)、四甘醇双(偏苯三酸酐)、六甘醇双(偏苯三酸酐)、新戊二醇双(偏苯三酸酐)、对苯二酚双(2-羟乙基)醚双(偏苯三酸酐)、2-苯基-5-(2,4-二甲苯基)-1,4-氢化醌双(偏苯三酸酐)、2,3-二氰基氢醌环丁烷-1,2,3,4-四羧酸二酐、1,2,3,4-环戊烷四羧酸二酐、1,2,4,5-环己烷四羧酸二酐、双环[2.2.1]庚烷-2,3,5,6-四羧酸二酐、双环[2.2.2]辛-7- 烯-2,3,5,6-四羧酸二酐、双环[2.2.2]辛烷-2,3,5,6-四羧酸二酐、2,3,5-三羧基-环戊基乙酸二酐、双环[2.2.1]庚烷-2,3,5-三羧基-6-乙酸二酐、十氢-1,4,5,8-二甲醇萘-2,3,6,7-四羧酸二酐、丁-1,2,3,4-四羧酸二酐、3,3′,4,4′-二环己基四羧酸二酐。这些四羧酸二酐可单独使用或两种以上(诸如:三种、四种、五种)组合使用。
该二胺的实例包括但不限于:3,3′-二氨基二苯砜、4,4′-二氨基二苯砜、3,3′-亚甲基二苯胺、4,4′-亚甲基二苯胺、2,2-双(4-氨基苯基)丙烷、2,2-双(4-氨基苯基)六氟丙烷、2,2′-双(三氟甲基)联苯胺、2,2′-二甲基联苯胺、3,3′-二羟基联苯胺、1,3-双(3-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、4,4′-双(4-氨基苯氧基)联苯、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,3-双[4-(3-氨基苯氧基)苯甲酰基]苯、4,4′-二氨基苯甲酰苯胺、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、5-氨基-2-(对氨基苯基)苯并噁唑、6-氨基-2-(对氨基苯基)苯并噁唑等。这些二胺可单独使用或两种以上(诸如:三种、四种、五种)组合使用。
在本发明中,考量其他特性,如图案形成性,该二氧化钛较佳地占该感光性聚酰亚胺树脂组合物的固体成分总重的30~70%,更佳为35~50%。
光自由基引发剂为感光树脂组合物中常用的引发剂。光自由基引发剂的实例可包括但不限于:肟衍生物等肟化合物、酮化合物(包含苯乙酮类、二苯甲酮类及噻吨酮类化合物)、三嗪类化合物、苯偶姻类化合物、茂金属化合物、三嗪类化合物或酰基膦化合物。这些引发剂可单独使用或两种以上(诸如:三种、四种、五种)组合使用。就曝光感度的观点而言,光自由基引发剂优选为酰基膦化合物或肟化合物。
肟衍生物等肟化合物的实例可包括但不限于:基于O-酰基肟的化合物、2-(邻苯甲酰基肟)-1-[4-(苯硫基)苯基]-1,2-辛二酮、1-(邻-乙酰基肟)-1-[9-乙基-6-(2-甲基苯甲酰基)-9H-咔唑-3-基]乙酮、O-乙 氧基羰基-α-氧基氨基-1-苯基丙-1-酮等。这些化合物可单独使用或两种以上(诸如:三种、四种、五种)组合使用。基于O-酰基肟的化合物的实例可包括但不限于:1,2-辛二酮、2-二甲基氨基-2-(4-甲基苄基)-1-(4-吗啉-4-基-苯基)-丁-1-酮、1-(4-苯基硫烷基苯基)-丁烷-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-苯基硫烷基苯基)-辛烷-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-苯基硫烷基苯基)-辛-1-肟-O-乙酸酯、1-(4-苯基硫烷基苯基)-丁-1-肟-O-乙酸酯等。这些基于O-酰基肟的化合物可单独使用或两种以上(诸如:三种、四种、五种)组合使用。酰基膦化合物的实例,包含双(2,4,6-三甲基苯甲酰基)苯基膦氧化物或2,4,6-三甲基苯甲酰基-二苯基氧膦,但不限于此。这些酰基膦化合物可单独使用,也可组合两种以上使用。
光自由基引发剂的含量较佳为主要树脂的0.1重量%至30重量%,更佳为1重量%至20重量%。当光自由基引发剂的含量在所述范围内,则在图案形成过程中曝光期间因聚酰亚胺充分固化,可以确保聚酰亚胺膜具有优异的可靠性,图案具有较优异的分辨率和紧密接触的耐热性,耐光性和耐化学性。
光自由基引发剂可以与光敏剂一起使用,该光敏剂能够通过吸收光并受激发而引起化学反应,然后传递其能量。光敏剂的实例可以包括但不限于:四乙二醇双-3-巯基丙酸酯、季戊四醇四-3-巯基丙酸酯、二季戊四醇四烷基-3-巯基丙酸酯等。这些光敏剂可单独使用或两种以上(诸如:三种)组合使用。
自由基聚合性化合物,为光自由基交联剂,其种类并无特别的限制。在本发明的一个较佳实施方式中,该自由基聚合性化合物为具有至少二个(甲基)丙烯酸酯基的化合物,诸如:具有二个(甲基)丙烯酸酯基的化合物、具有三个(甲基)丙烯酸酯基的化合物、具有四个(甲基)丙烯酸酯基的化合物、具有五个(甲基)丙烯酸酯基的化合物或具有六个(甲基)丙烯酸酯基的化合物。该具有至少二个(甲基)丙烯酸酯基的化合物的实例可包括但不限于:二甲基丙烯酸乙二醇酯;双酚A的EO修饰二丙烯酸酯(n=2-50)(EO是环氧乙烷,n是所加入的 环氧乙烷的摩尔数);双酚F的EO修饰二丙烯酸酯;BLEMMER
Figure PCTCN2019072780-appb-000003
Figure PCTCN2019072780-appb-000004
(NOF Co.,Ltd。);Aronix
Figure PCTCN2019072780-appb-000005
和/或
Figure PCTCN2019072780-appb-000006
(东亚合成化学工业株式会社制);KAYARAD
Figure PCTCN2019072780-appb-000007
Figure PCTCN2019072780-appb-000008
和/或
Figure PCTCN2019072780-appb-000009
(Nippon Kayaku Co.,Ltd.);
Figure PCTCN2019072780-appb-000010
和/或
Figure PCTCN2019072780-appb-000011
(Osaka Organic Chemical Ind.,Ltd.);三羟甲基丙烷三丙烯酸酯(TMPTA);羟甲基丙烷四丙烯酸酯;甘油三羟丙基醚三丙烯酸酯;三乙氧基三羟甲基丙烷三丙烯酸酯;三羟甲基丙烷三甲基丙烯酸酯;三(2-羟基乙基)异氰酸酯三丙烯酸酯(THEICTA);季戊四醇三丙烯酸酯;季戊四醇六丙烯酸酯;Aronix
Figure PCTCN2019072780-appb-000012
Figure PCTCN2019072780-appb-000013
和/或
Figure PCTCN2019072780-appb-000014
(东亚合成化学工业株式会社);KAYARAD
Figure PCTCN2019072780-appb-000015
Figure PCTCN2019072780-appb-000016
和/或
Figure PCTCN2019072780-appb-000017
(日本化药株式会社);
Figure PCTCN2019072780-appb-000018
和/或
Figure PCTCN2019072780-appb-000019
(Osaka Yuki Kayaku Kogyo Co.,Ltd)。
在本发明另一较佳实施方式中,该自由基聚合性化合物为具有(甲基)丙烯酸酯基的聚酰胺酸酯,即具有甲基丙烯酸酯(CH 2=C(CH 3)-COO-)的聚酰胺酸酯或具有丙烯酸酯基(CH 2=CH-COO-)的聚酰胺酸酯。在一个较佳实施方式中,该具有(甲基)丙烯酸酯基的聚酰胺酸酯通过四羧酸二酐、甲基丙烯酸-2-羟基乙酯及二胺反应而得。
在感光性聚酰亚胺树脂组合物中,就良好的自由基聚合性与耐热性的观点而言,相对于感光性聚酰亚胺树脂组合物的总固体成分,自由基聚合性化合物的含量较佳为1质量%~50质量%。下限更佳为5质量%以上。上限更佳为40质量%以下。自由基聚合性化合物可单独使用一种,也可将两种以上(诸如:两种、三种、四种)混合使用,较佳是混合三种自由基聚合性化合物来使用,更佳是三种中至少一种为具有(甲基)丙烯酸酯基的聚酰胺酸酯。
在本发明中,该具有(甲基)丙烯酸酯基的聚酰胺酸酯在自由基聚合性化合物中的含量较佳为10重量%~98重量%,更佳为30重量%~95重量%,特佳为50重量%~90重量%。若该具有(甲基)丙烯酸酯基的聚酰胺酸酯的含量介于所述范围内,则可形成硬化性及耐热性更优异的硬化膜。自由基聚合性化合物可仅使用一种,也可使用两种以上。当使用两种以上时,较佳为总量成为所述范围。
当自由基聚合性化合物的含量在上述范围内时,其通过光自由基引发剂及UV辐射照射所起始的自由基反应而产生的交联键,可以改善图案形成能力。另外,在图案形成过程中可以充分发生曝光固化,并且可以改善碱性显影液的对比性。
在本发明中,该溶剂并无特别限制,只要其能溶解该感光性聚酰亚胺。该溶剂的实例包括但不限于:乙酸乙酯、乙酸-正丁酯、γ-丁内酯、ε-己内酯、二乙二醇二甲醚、四氢呋喃、乙二醇单甲醚、乙二醇单乙醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、及丙二醇单丙醚乙酸酯、甲基乙基酮、环己酮、环戊酮、N-甲基吡咯啶酮、二甲基甲酰胺、二甲基亚砜或N,N-二甲基乙酰胺(DMAc)。这些溶剂可单独使用或两种以上(诸如:两种、三种或四种)组合使用。就改良涂布表面状态的观点而言,将两种以上的溶剂混合较佳。当感光性树脂组合物含有溶剂时,就涂布性的观点而言,溶剂的含量较佳为感光性树脂组合物的总固体成分的5质量%~80质量%,更佳为5质量%~70质量%,特佳为10质量%~60质量%。溶剂可仅为一种,也可为两种以上。当含有两种以上的溶剂时,较佳为总量在所述范围。
本发明的感光性聚酰亚胺树脂组合物可添加或不添加添加剂。该添加剂的选择可视本发明的感光性聚酰亚胺树脂组合物的应用而定。该添加剂的实例包括但不限于:高级脂肪酸衍生物、界面活性剂、无机粒子、硬化剂、硬化触媒、填充剂、抗氧化剂、紫外线吸收剂、抗凝聚剂、流平剂或这些添加剂两种以上的组合。当调配这 些添加剂时,较佳为将其总调配量设为感光性树脂组合物的固体成分的10质量%以下。
本发明还提供一种聚酰亚胺膜,其由前述的树脂组合物所形成。
在一个较佳实施方式中,该聚酰亚胺膜经260℃回焊前后的色差ΔE*ab为2以下。
在一个较佳实施方式中,该聚酰亚胺膜经200℃烘烤2小时前后的色差ΔE*ab为2以下。
在一个较佳实施方式中,该聚酰亚胺膜的硬度为7H以上。
在一个较佳实施方式中,该聚酰亚胺膜具有孔径为100μm以下的孔图案。
本发明层间绝缘膜及保护膜的制备,可以通过旋转涂布或流延涂布等涂布方法,将该感光性聚酰亚胺树脂组合物涂布在基板上,再经预烤(prebake)方式将溶剂去除而形成预烤涂膜。其中,预烤的条件,依各成分的种类、配合比率而不同,通常为温度在80~120℃间,进行5~15分钟。预烤后,将该涂膜在光罩下进行曝光,曝光所使用的光线,以g线、h线、i线等的紫外线为佳,而紫外线照射装置可为(超)高压水银灯及金属卤素灯。然后在20~40℃的温度下浸渍于显影液中,历时1~2分钟,以去除不要的部分而形成特定的图案。该显影液的实例包括但不限于:甲醇、乙醇、丙醇、异丙醇、丁醇、乙酸乙酯、乙酸正丁酯、γ-丁内酯、ε-己内酯、二乙二醇二甲醚、四氢呋喃、乙二醇单甲醚、乙二醇单乙醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、丙二醇单丙醚乙酸酯、甲基乙基酮、环己酮、环戊酮、N-甲基吡咯啶酮、二甲基甲酰胺、二甲基亚砜或N,N-二甲基乙酰胺等有机溶剂。该显影液也可为前述有机溶剂两种以上的组合。
使用上述有机溶剂所构成的显影液时,通常在显影后以有机溶剂洗净,再以压缩空气或压缩氮气风干。然后,使用热板或烘箱等加热装置进行后烤(postbake)处理,该后烤处理的温度通常为180~ 250℃。经过以上的处理步骤后即可形成保护膜。
因此,本发明还提供一种基板,其包含前述的聚酰亚胺膜。
为突显本案功效,发明人特依下文所载方式完成实施例及比较例,以下实施例及比较例均为发明人的实验数据,不属于现有技术的范畴。以下实施例及比较例将对本发明做进一步说明,但是这些实施例及比较例并非用以限制本发明的范围,任何熟悉本发明技术领域者,在不违背本发明的精神下所做的改变及修饰,均属本发明的范围。
合成例1:感光性聚酰亚胺的制备
将62.12g(0.194mole)的2,2′-双(三氟甲基)联苯胺(TFMB)及500g的DMAc置入三颈烧瓶内。在30℃下搅拌至完全溶解后,再加入84.86g(0.200mole)的丙二醇双(偏苯三酸酐)(TMPG),然后持续搅拌并在25℃下反应24小时,可得到聚酰胺酸溶液。然后再添加23.00g(0.290mole)的吡啶及59.4g(0.582mole)的醋酸酐,然后持续搅拌并在25℃下反应24小时。反应结束后,在5升的水中使聚酰亚胺沉淀,并以5000rpm的速度将水与聚酰亚胺的混合物搅拌15分钟。对聚酰亚胺进行滤取,再次投入至4升的水中进而搅拌30分钟并再次进行过滤。然后,在减压下,在45℃下将所获得的聚酰亚胺干燥3日,获得经干燥的聚酰亚胺(TMPG-TFMB PI(A1))。将所得的A1以 1H-NMR测定的结果显示于下(以不重复的结构单元定义其氢数比例)。 1H-NMR(500MHz,DMSO-d 6,δppm):8.47-8.20(4H,m),8.15-7.70(6H,m),7.47-7.41(2H,m),4.45-4.38(4H,m),2.48-2.39(2H,m);FT-IR(cm -1):3066,2971,1778,1726,1601,1486,1426,1310,1273,1138,1078,840,722.
合成例2:具有甲基丙烯酸酯基的聚酰胺酸酯的制备
[丙二醇双(偏苯三酸酐)(TMPG)、2,2′-双(三氟甲基)联苯胺(TFMB)及甲基丙烯酸-2-羟基乙酯(HEMA)的具有丙烯酸酯基的聚酰胺酸酯(D3)的合成]
在四颈烧瓶中,将16.97g(40.0毫摩尔)的丙二醇双(偏苯三酸 酐)(TMPG)、10.94g(84.0毫摩尔)甲基丙烯酸-2-羟基乙酯(HEMA)、0.04g(0.4毫摩尔)的对苯二酚、3.16g(84.0毫摩尔)的吡啶及80mL的四氢呋喃依序加入,在50℃下搅拌3小时,自加热开始几分钟后获得透明的溶液。将反应混合物冷却至室温。然后,将反应混合物冷却至-10℃,一面将温度保持为-10℃±4℃,一面历时10分钟添加11.9g(100.0毫摩尔)的氯化亚砜。在添加氯化亚砜期间,粘度增加。利用50mL的二甲基乙酰胺进行稀释后,在室温下将反应混合物搅拌2小时。继续将温度保持为-10℃±4℃,使用11.62g(200.0毫摩尔)的作为中和剂的环氧丙烷中和多余盐酸,再历时20分钟将使12.75g(39.8毫摩尔)的2,2′-双(三氟甲基)联苯胺(TFMB)溶解在100mL的二甲基乙酰胺所形成的溶液滴加至反应混合物中,在室温下将反应混合物搅拌15小时。反应结束后,在5升的水中使具有甲基丙烯酸酯基的聚酰胺酸酯沉淀,并以5000rpm的速度将水与具有甲基丙烯酸酯基的聚酰胺酸酯的混合物搅拌15分钟。对具有甲基丙烯酸酯基的聚酰胺酸酯进行滤取,再次投入至4升的水中进而搅拌30分钟并再次进行过滤。然后,在减压下,在45℃下将所获得的具有甲基丙烯酸酯基的聚酰胺酸酯干燥3日,获得经干燥的具有甲基丙烯酸酯基的聚酰胺酸酯(HEMA-TMPG-TFMB PAE(D3))。将所得的D3以 1H-NMR测定的结果显示于下(以不重复的结构单元定义其氢数比例)。 1H-NMR(500MHz,DMSO-d 6,δppm):11.10-11.07(2H,m,NH),8.46-8.43(2H,m),8.39-8.32(2H,m),8.12-8.01(2H,m),7.60-7.38(4H,m),7.30-7.23(2H,m),4.49-4.30(12H,m),2.49-2.40(2H,m),1.84-1.80(6H,m);FT-IR(cm -1):2923,2821(C-H),1780(C=O),1725(C=O),1648(CH2=CH),1615,1485,1425,1366,1273,1241,1198,1134,1078,842,742.
实施例1-6及比较例1-4:感光性聚酰亚胺树脂组合物的制备
感光性聚酰亚胺树脂组合物所用的成分如下所示。将下述记载的成分按表1所载的重量比与溶剂混合,制成固含量30%的溶液,即为感光性聚酰亚胺树脂组合物的涂布液。
成分A1:TMPG-TFMB PI
成分B1:粒径为0.4μm的TiO2
成分B2:粒径为5.0μm的TiO2
成分B3:粒径为10.0μm的TiO2
成分B4:粒径为0.1μm的TiO2
成分B5:粒径为12.0μm的TiO2
成分C1:Irgacure 184
成分D1:聚二季戊四醇六丙烯酸酯(DPHA)
成分D2:PDBE-450A(NOF)
成分D3:HEMA-TMPG-TFMB PAE
成分E1:DMAc
评价结果
<图案形成性>
感光性树脂组合物经涂膜在铜箔基板上,经由90度5分钟表干制得薄膜,经由光罩曝光后,利用环戊酮对经曝光的感光性聚酰亚胺树脂组合物层进行60秒钟显影。通过以下的基准来评价所形成的图案是否具有良好边缘锐度的线宽。感光性聚酰亚胺树脂组合物层的线宽越小,表示光照射部与非光照射部对于显影液的溶解性之差变得越大,而成为较佳的结果。另外,相对于曝光能量的变化而线宽的变化越小,表示曝光宽容度越广,而成为较佳的结果。
以光学显微镜来观察所形成的粘着剂图案后,将形成有线宽/间距宽=100μm/100μm以下的细线图案的情形设为A,将形成有线宽/间距宽=超过100μm/100μm的细线图案的情形设为B,进行图案形成性的评估。评估结果如表1所示。
<反射率>
使用积分球式分光仪(X-RITE SP60)进行测定,在波长550nm下测试感光性聚酰亚胺树脂组合物所形成的聚酰亚胺膜的反射率。
<黄度>
对于感光性聚酰亚胺树脂组合物所形成的聚酰亚胺膜,使用分光测色计CM-600d(Konica Minolta Sensing社制)测定其(L、a、b)色系中的b值。
<耐热黄变>
使用分光测色计CM-600d(Konica Minolta Sensing社制)测定其(L、a、b)色系中经260℃的热处理,并持续10分钟后,与未经热处理前的样品为基准测定所得的ΔE值。
<硬度>
取将笔芯磨平的B至9H的铅笔以约45度的角度压在试片上,记录不产生涂膜剥离的铅笔的硬度。
实施例1至6及比较例1至4的感光性聚酰亚胺树脂组合物的配方,以及其所形成的聚酰亚胺膜的测试结果如表1所示。
表1
Figure PCTCN2019072780-appb-000020
Figure PCTCN2019072780-appb-000021
注:表1中配方组成的单位为重量份
本发明实施例及比较例所制得的聚酰亚胺膜因添加有作为白色颜料的二氧化钛,而呈白色,且具遮蔽性。如表1所示,本发明的感光性聚酰亚胺树脂组合物所形成的聚酰亚胺膜在黄度、反射率、硬度、耐热性方面具有优异的表现。
综上所述,本发明的感光性聚酰亚胺树脂组合物经预烤、曝光、显影及后烤处理后,所形成的保护膜可同时具备较高反射率、低热黄变;且该硬化膜可适用于类载板、液晶显示器、有机电激发光显示器、半导体元件或印刷电路板等所含的基板上。
以上所述内容,仅为本发明的较佳实施例而已,不能以此限定本发明实施的范围,即只要是依本发明权利要求及发明说明内容所作的简单的等效变化与修饰,都仍属本发明专利涵盖的范围内。

Claims (20)

  1. 一种感光性聚酰亚胺树脂组合物,其包含:(a)感光性聚酰亚胺,其由式(1)所表示;(b)二氧化钛,其粒径为0.2微米~10微米;(c)光自由基引发剂;(d)自由基聚合性化合物;(e)溶剂,其用于溶解该感光性聚酰亚胺,
    Figure PCTCN2019072780-appb-100001
    其中,X来源于四羧酸二酐,Y来源于二胺,m为1~5000中的正整数。
  2. 如权利要求1所述的树脂组合物,其中该四羧酸二酐为3,3′,4,4′-联苯四羧酸二酐、3,3′,4,4′-二苯甲酮四羧酸二酐、4,4′-氧联二邻苯二甲酸酐、双(3,4-二羧基苯基)甲烷二酐、2,2-二(3,4-二羧基苯基)丙烷二酐、2,2-双(3,4-二羧基苯基)丙烷二酐、1,3-双(3,4-二羧基苯氧基)苯二酐、1,4-双(3,4-二羧基苯氧基)苯二酐、4,4′-双(3,4-二羧基苯氧基)联苯二酐、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐、乙二醇双(偏苯三酸酐)、丙二醇双(偏苯三酸酐)、1,2-丙二醇双(偏苯三酸酐)、丁二醇双(偏苯三酸酐)、2-甲基-1,3-丙二醇双(偏苯三酸酐)、二丙二醇双(偏苯三酸酐),2-甲基-2,4-戊二醇双(偏苯三酸酐)、二甘醇双(偏苯三酸酐)、四甘醇双(偏苯三酸酐)、六甘醇双(偏苯三酸酐)、新戊二醇双(偏苯三酸酐)、对苯二酚双(2-羟乙基)醚双(偏苯三酸酐)、2-苯基-5-(2,4-二甲苯基)-1,4-氢化醌双(偏苯三酸酐)、2,3-二氰基氢醌环丁烷-1,2,3,4-四羧酸二酐、1,2,3,4-环戊烷四羧酸二酐、1,2,4,5-环己烷四羧酸二酐、双环[2.2.1]庚烷-2,3,5,6-四羧酸二酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、双环[2.2.2]辛烷-2,3,5,6-四羧酸二酐、2,3,5-三羧基-环戊基乙酸二酐、双环[2.2.1]庚烷-2,3,5-三羧基-6-乙酸二酐、十氢-1,4,5,8-二甲醇萘-2,3,6,7-四羧酸二酐、丁-1,2,3,4-四羧酸二酐、 3,3′,4,4′-二环己基四羧酸二酐或前述四羧酸二酐任意二种以上的组合。
  3. 如权利要求1所述的树脂组合物,其中该二胺为3,3′-二氨基二苯砜、4,4′-二氨基二苯砜、3,3′-亚甲基二苯胺、4,4′-亚甲基二苯胺、2,2-双(4-氨基苯基)丙烷、2,2-双(4-氨基苯基)六氟丙烷、2,2′-双(三氟甲基)联苯胺、2,2′-二甲基联苯胺、3,3′-二羟基联苯胺、1,3-双(3-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、4,4′-双(4-氨基苯氧基)联苯、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,3-双[4-(3-氨基苯氧基)苯甲酰基]苯、4,4′-二氨基苯甲酰苯胺、2,2-双(3-氨基-4-羟基苯基)六氟丙烷、5-氨基-2-(对氨基苯基)苯并噁唑、6-氨基-2-(对氨基苯基)苯并噁唑或前述二胺任意二种以上的组合。
  4. 如权利要求1所述的树脂组合物,其中该二氧化钛的粒径为0.3微米~5微米。
  5. 如权利要求1所述的树脂组合物,其中该二氧化钛占该感光性聚酰亚胺树脂组合物的固体成分总重的30~70%。
  6. 如权利要求5所述的树脂组合物,其中该二氧化钛占该感光性聚酰亚胺树脂组合物的固体成分总重的35~50%。
  7. 如权利要求1所述的树脂组合物,其中该自由基聚合性化合物为具有至少二个(甲基)丙烯酸酯基的化合物。
  8. 如权利要求1所述的树脂组合物,其中该自由基聚合性化合物为具有(甲基)丙烯酸酯基的聚酰胺酸酯。
  9. 如权利要求8所述的树脂组合物,其中该具有(甲基)丙烯酸酯基的聚酰胺酸酯在自由基聚合性化合物中的含量为10重量%~98重量%。
  10. 如权利要求1所述的树脂组合物,其所形成的聚酰亚胺膜在波长450nm下的反射率为85%以上。
  11. 如权利要求1所述的树脂组合物,其所形成的聚酰亚胺膜的经260℃回焊前后的色差ΔE*ab为2以下。
  12. 如权利要求1所述的树脂组合物,其所形成的聚酰亚胺膜的经200℃烘烤2小时前后的色差ΔE*ab为2以下。
  13. 如权利要求1所述的树脂组合物,其所形成的聚酰亚胺膜的硬度为7H以上。
  14. 如权利要求1所述的树脂组合物,其所形成的聚酰亚胺膜具有孔径为100μm以下的孔图案。
  15. 一种聚酰亚胺膜,其由权利要求1所述的树脂组合物所形成。
  16. 如权利要求15所述的聚酰亚胺膜,其经260℃回焊前后的色差ΔE*ab为2以下。
  17. 如权利要求15所述的聚酰亚胺膜,其经200℃烘烤2小时前后的色差ΔE*ab为2以下。
  18. 如权利要求15所述的聚酰亚胺膜,其硬度为7H以上。
  19. 如权利要求15所述的聚酰亚胺膜,其具有孔径为100μm以下的孔图案。
  20. 一种基板,其包含如权利要求15所述的聚酰亚胺膜。
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