CN108780275A - Photosensitive film - Google Patents

Photosensitive film Download PDF

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Publication number
CN108780275A
CN108780275A CN201780019777.4A CN201780019777A CN108780275A CN 108780275 A CN108780275 A CN 108780275A CN 201780019777 A CN201780019777 A CN 201780019777A CN 108780275 A CN108780275 A CN 108780275A
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film
general formula
indicate
photosensitive film
carbon atom
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CN201780019777.4A
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CN108780275B (en
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池田芳史
小山祐太朗
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Toray Industries Inc
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Toray Industries Inc
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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
    • G03F7/022Quinonediazides
    • G03F7/023Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02Monomers containing only one unsaturated aliphatic radical
    • C08F12/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22Oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/28Condensation with aldehydes or ketones
    • 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
    • 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
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions 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
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/027Non-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
    • 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
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/16Coating processes; Apparatus therefor
    • G03F7/168Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/20Exposure; Apparatus therefor
    • 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
    • G03F7/26Processing photosensitive materials; Apparatus therefor

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  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Materials For Photolithography (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

The cured film of high-fire resistance can be obtained, with good pattern processability (high sensitive) and with the good adaptation i.e. photosensitive film of plyability with substrate in offer.Photosensitive film contains:(A1) alkali soluble resins of the structural unit indicated with general formula (1);(A2) include the alkali soluble resins selected from polyimides, polybenzoxazole, polyamidoimide, their precursor and one or more of their copolymer;(B) photoacid generator;And (C) thermal cross-linking agent.In general formula (1), R1Indicate that hydrogen atom or the alkyl of carbon atom number 1~5, a indicate that the integer in the range of 0~4, b indicate the integer in the range of 1~3, R2For any one of hydrogen atom, methyl, ethyl, propyl.

Description

Photosensitive film
Technical field
The present invention relates to photosensitive films.More specifically, it is related to the surface protection film suitable for semiconductor component surfaces, layer insulation Film, organic electroluminescent device insulating layer photosensitive film.
Background technology
There is excellent heat resistance, electrical insulating property as the resin of representative using polyimides, polybenzoxazole, therefore have been used for half The surface protection film of conductor element, the insulating layer etc. of interlayer dielectric, organic electroluminescent device.In recent years, with semiconductor The miniaturization of element also requires several μm of horizontal resolution ratio for surface protection film, interlayer dielectric etc..Therefore, such With on the way, mostly using can microfabrication positive type photosensitive polyimide resin composition, positive light sensitivity polybenzoxazole Resin combination.
In the manufacturing process of common semiconductor devices, semiconductor element is formed on substrate, is formed with Si, SiN on substrate For the passivating film of representative, photosensitive layer is formed on passivating film, is then thermally dried using heating plate etc., by exposing and showing Shadow and form pattern.After forming pattern, the heat treatment using high temperature is carried out, makes its solidification, insulating layer is consequently formed.
All the time, circular substrate has been used in the formation of semiconductor element, but in recent years, with the enlargement of substrate, So that rectangular substrate is used.
As the method for forming photosensitive layer on substrate, have:The method for being coated with resin combination using spin-coating method;Substrate is applied The method that photosensitive film crimping is laminated by heating.When forming insulating layer in large-scale square substrate, in order to improve shape Film thickness uniformity after, the method being usually laminated using photosensitive film.
As the positive type photosensitive polyimide used in resin combination, photosensitive film, it is known that the substance based on polyimides (such as patent document 1), the substance (such as patent document 2) based on polycarboxylated styrene and by polyimides and poly- hydroxy benzenes The substance (such as patent document 3) that ethylene is obtained by mixing.
In addition, as photosensitive film, it is proposed that using the technology (such as patent document 4) of phenolic resin, use glass transition The technology (such as patent document 5) of the low polyimides of temperature.
Existing technical literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2014-71374 bulletins
Patent document 2:Japanese Unexamined Patent Publication 2006-154779 bulletins
Patent document 3:Japanese Unexamined Patent Publication 2014-137523 bulletins
Patent document 4:Japanese Unexamined Patent Publication 2015-19006 bulletins
Patent document 5:International Publication 2011/059089
Invention content
The subject that the invention solves
As previously mentioned, when forming insulating layer in square substrate, in order to improve the film thickness uniformity after being formed, usually use feeling The method that photosensitiveness film is laminated.For photosensitive film, in addition to the high drawing for being required to assign cured film is forthright, heat-resisting Property etc. other than mechanical properties, it is also desirable to have good pattern processability (high sensitive), and require good with substrate Adaptation, that is, plyability.
However, for film obtained from such resin combination of the use based on polyimides disclosed in Patent Documents 1 to 3 and Speech, flexibility is insufficient, there is the case where cracking etc. when being laminated connecing membrane pressure to substrate application heat, plyability is not Fully.In addition, being disclosed in patent document 4 for the purpose for improving mobility and using the technology of phenolic resin, but exist solid Low this problem of heat resistance of film after change.In addition, disclosing the skill using the low polyimides of softening point in patent document 5 Art, but exist and cannot get high-fire resistance this problem.
Therefore, the present invention provide can be obtained high-fire resistance cured film, have good pattern processability (high sensitive) and Photosensitive film with good adaptation, that is, plyability with substrate.
Means for solving the problems
To solve the above subject, photosensitive film of the invention has following compositions.That is, photosensitive film, contains:(A1) have The alkali soluble resins for the structural unit that general formula (1) indicates;(A2) include sub- selected from polyimides, polybenzoxazole, polyamide acyl The alkali soluble resins of amine, their precursor and one or more of their copolymer;(B) photoacid generator;And (C) heat is handed over Join agent.
[chemical formula 1]
(in general formula (1), R1Indicate that hydrogen atom or the alkyl of carbon atom number 1~5, a indicate that the integer in the range of 0~4, b indicate Integer in the range of 1~3, R2For any one of hydrogen atom, methyl, ethyl, propyl.)
The effect of invention
In accordance with the invention it is possible to obtain there is good pattern processability (high sensitive) and with good with substrate The photosensitive film of adaptation, that is, plyability.In addition, photosensitive film according to the present invention, can obtain high elongation rate and high-fire resistance Cured film.
Description of the drawings
[Fig. 1] is an example of the cross-sectional for the semiconductor devices for having used the photosensitive film of the present invention.
[Fig. 2] is an example of the sectional view of the coiler part for the inductor arrangement for having used the photosensitive film of the present invention.
[Fig. 3] is an example of the sectional view of the hollow portion for the acoustic wave device for having used the photosensitive film of the present invention.
[Fig. 4] be used the present invention photosensitive film, on substrate with layer difference semiconductor devices sectional view one Example.
Specific implementation mode
The present invention is photosensitive film, is contained:Above-mentioned (A1) has the alkali soluble resins of the structural unit of general formula (1) expression; (A2) comprising one in polyimides, polybenzoxazole, polyamidoimide, their precursor and their copolymer Kind or more alkali soluble resins;(B) photoacid generator;And (C) thermal cross-linking agent.Hereinafter, sometimes respectively save slightly (A1) resin, (A2) resin, (B) ingredient, (C) ingredient.
The photosensitive film of the present invention includes the alkali soluble resins that above-mentioned (A1) has the structural unit of general formula (1) expression.It is above-mentioned logical R in formula (1)1Indicate that hydrogen atom or the alkyl of carbon atom number 1~5, a indicate that the integer in the range of 0~4, b indicate 1~3 Integer in range, R2Indicate any one of hydrogen atom, methyl, ethyl, propyl.By containing (A1) resin, can improve The susceptibility of photosensitive film.
The structural unit that above-mentioned general formula (1) indicates for example can be by using known method (such as Japanese Patent No. 5659259 The method that bulletin is recorded) so that a part for alkoxy and following polymer is carried out addition reaction and is obtained, the polymer is profit By known method by 4-Vinyl phenol, hydroxy styrenes, o-hydroxystyrene, to isopropenyl phenol, isopropyl alkene The aromatic ethenyl compounds and styrene, o-methyl-benzene second with phenolic hydroxyl such as base phenol, adjacent isopropenyl phenol The aromatic ethenyl compounds such as alkene, m-methyl styrene, p-methylstyrene are individually or among the above two or more are gathered Obtained from conjunction.
Aromatic ethenyl compound with phenolic hydroxyl preferably uses 4-Vinyl phenol and/or hydroxy styrenes, Aromatic ethenyl compound preferably uses styrene.
For above-mentioned (A1) have general formula (1) indicate structural unit alkali soluble resins for, from further increase susceptibility, From the aspect of the deliquescent convenience in alkaline-based developer can be adjusted, preferably also there is general formula (2) and general formula (3) table At least either in the structural unit shown.In addition, from the viewpoint of dissolubility from alkaline-based developer, general formula (3) Structural unit is preferably 50mol% or less.
[chemical formula 2]
(in general formula (2), R3Indicate that hydrogen atom or the alkyl of carbon atom number 1~5, e indicate the integer in the range of 1~5.)
[chemical formula 3]
(in general formula (3), R4Indicate hydrogen atom or the alkyl of carbon atom number 1~5.)
For the alkoxy alkane (CH in above-mentioned (A1) resin2OR2) base Drug delivery rate for, from the viewpoint of the heat resistance after solidification Consider, preferably with respect to for every 1 hydroxy styrene be 10mol% or more Drug delivery rate, more preferably 20mol% with On.From the viewpoint of improving resolution ratio, preferably 70mol% is hereinafter, more preferably 50mol% or less.
From make the pattern in unexposed portion from the viewpoint of being formed in this way in the case of not dissolving out, above-mentioned (A1) resin through polyphenyl The weight average molecular weight (Mw) of ethylene conversion is preferably 3,000 or more.In addition, from the alkali soluble solution for the residue for maintaining to reduce exposure portion From the viewpoint of property, preferably 60,000 hereinafter, more preferably 25, and 000 or less.
The above-mentioned weight average molecular weight (Mw) through polystyrene conversion refers to using GPC (gel infiltrations based on what polystyrene converted Chromatography) measure and calculate value.
The photosensitive film of the present invention contain (A2) include selected from polyimides, polybenzoxazole, polyamidoimide, before them The alkali soluble resins of one or more of body and their copolymer.
Above-mentioned (A2) resin may include polyimides, polybenzoxazole, polyamidoimide, their precursor and being total to for they It is arbitrary two or more in polymers, it also may include the copolymer with the two or more repetitive units in these.In addition, (A2) Resin preferably has the substituent group reacted with the alkoxyalkyl of above-mentioned (Al) resin.The alkoxyalkyl of so-called (Al), especially Refer to alkoxy methyl.(A2) excellent as long as there is the structure of resin the substituent group reacted with alkoxyalkyl to be not particularly limited It is selected in the group that main chain or end have more than one in carboxyl, phenolic hydroxyl, sulfonic group and mercapto.
It is reacted upon thermal curing by the alkoxyalkyl and (A2) resin of (Al) resin, can fully maintain heat resistance And mechanical property, therefore can be achieved at the same time good pattern processability that (A1) resin has and the height that (A2) resin has is resistance to Hot and high mechanical property.From the viewpoint of pattern processability, 100 mass of total amount relative to (A1) resin and (A2) resin Part, the content of (A2) resin is preferably 5 mass parts or more, more than more preferably 10 mass parts.In addition, special from heat resistance and machinery From the viewpoint of property, preferably 90 is below mass part, and more preferably 70 is below mass part.
At least either in the structural unit that above-mentioned (A2) resin is preferably indicated with general formula (4) and (5).
[chemical formula 4]
(in general formula (4), R5Indicate two~quadrivalent organic radical group of carbon atom number 4~40.R6Indicate carbon atom number 20~100 Bivalent organic group.n1Indicate the integer in the range of 10~100,000.)
[chemical formula 5]
(in general formula (5), R5Indicate two~quadrivalent organic radical group of carbon atom number 4~40.R6Indicate carbon atom number 20~100 Bivalent organic group.R7Indicate hydrogen or the organic group of carbon atom number 1~20.n2Indicate whole in the range of 10~100,000 Number, p, q indicate the integer for meeting 0≤p+q≤2.)
In addition, in general formula (4) and (5), R5Indicate the alicyclic structure with monocyclic or fused polycyclic, carbon atom number 4~ 40 two~quadrivalent organic radical group.R5In, as monocyclic or the alicyclic structure of fused polycyclic, preferably comprise selected from following logical 1 or more organic group in formula (6)~(9).
[chemical formula 6]
(in general formula (6)~(9), R8~R53The monovalence for each independently representing hydrogen atom, halogen atom or carbon atom number 1~3 has Machine group.For the monovalent organic group of carbon atom number 1~3, the hydrogen atom for including in the organic group can be by halogen original Son substitution.)
In addition, the R in general formula (4) and (5)5Organic group for the acid dianhydride used from the raw material as resin.
It is used in the present invention to include two of the carbon atom number 4~40 with monocyclic or the alicyclic structure of fused polycyclic The acid dianhydride of~quadrivalent organic radical group, specifically, 1,2,3,4- cyclobutanetetracarboxylic dianhydrides, dimethyl -1 1,2- can be enumerated, 2,3,4- cyclobutanetetracarboxylic dianhydrides, 1,2,3,4- tetramethyls -1,2,3,4- cyclobutanetetracarboxylic dianhydrides, 1,2,4,5- hexamethylenes Compound as tetracarboxylic acid dianhydride.
In general formula (4) and (5), as R5In with 1~4 aromatic ring, two~quadrivalent organic radical of carbon atom number 4~40 The preferred structure of group, can enumerate from Pyromellitic Acid, 3,3 ', 4,4 '-bibenzene tetracarboxylics, 2,3,3 ', 4 '-bibenzene tetracarboxylics, 2, 2 ', 3,3 '-bibenzene tetracarboxylics, 3,3 ', 4,4 '-benzophenone tetracarboxylics, 2,2 ', 3,3 '-benzophenone tetracarboxylics, 2,2- are bis- Bis- (2, the 3- dicarboxyphenyi) hexafluoropropane of (3,4- dicarboxyphenyi) hexafluoropropane, 2,2-, bis- (3, the 4- dicarboxyl benzene of 1,1- Base) ethane, bis- (2, the 3- dicarboxyphenyi) ethane of 1,1-, bis- (3,4- dicarboxyphenyi) methane, bis- (2,3- dicarboxyphenyis) Methane, bis- (3,4- dicarboxyphenyi) sulfones, bis- (3,4- dicarboxyphenyi) ethers, 1,2,5,6- naphthalenetetracarbacidic acidics, 2,3,6,7- naphthalenes four Formic acid, 2, except being tied obtained from decarboxylate in the aromatic tetracarboxylics such as 3,5,6- pyridine tetracarboxylic acids, 3,4,9,1O- tetracarboxylic acids Structure, a part of hydrogen atom alkyl of 1~4 carbon atom number 1~20, fluoroalkyl, alkoxy, ester group, nitro, cyanogen by them Structure etc. obtained from base, fluorine atom, chlorine atom substitution.
From high elongation rate, improve the plyability of film and substrate from the viewpoint of, by the R in general formula (4) and (5)5It is set as When 100mol%, R5In monocyclic or the alicyclic structure of fused polycyclic be preferably 10mol% or more, more preferably 30mol% or more.From the viewpoint of available solution rate appropriate in developer solution is such, preferably 80mol% with Under, more preferably 60mol% or less.
For example, for the total amount 100mol% of general formula (4) and the repetitive unit of (5), R5With 70mol% monocyclics or The alicyclic structure of fused polycyclic and with 30mol% have aromatic ring quadrivalent organic radical group when, be calculated as having The alicyclic structure of 70mol% monocyclics or fused polycyclic.At this point, R5In there are two above monocyclic or fused polycyclic When alicyclic structure, it is calculated as 70mol%.
In addition, the R in general formula (4) and (5)6It is preferably provided with the organic group of the polyether structure indicated with the following general formula (10).
[chemical formula 7]
(in formula, R54~R57Each independently represent the alkylidene of carbon atom number 1~6.R58~R65Each independently represent hydrogen, The alkyl of fluorine or carbon atom number 1~6.Wherein, the structure indicated in the bracket of repetitive unit x and table in the bracket of repetitive unit y The structure shown is different.In addition, the structure indicated in the bracket of repetitive unit z and the structure indicated in the bracket of repetitive unit y are each From difference.X, y, z each independently represents 0~35 integer.) in addition, R in general formula (4) and (5)6To come from as resin The organic group of diamines that uses of raw material.
The diamines used in the present invention for including the organic group with polyether structure, specifically, can enumerate " JEFFAMINE " (registered trademark) HK-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D- 400, D-2000, D-4000, " ELASTAMINE " (registered trademark) RP-409, RP-2009, RT-1000, HT-1100, HE- 1000, the aliphatic diamines such as HT-1700 (being above trade name, HUNTSMAN (strain) systems).By with polyether structure, being endowed Meltbility when hydrophily and high temperature, therefore improved with the plyability of substrate, and it is endowed flexibility, therefore elongation improves, It is reduced additionally, due to elasticity modulus, therefore the warpage of chip is inhibited, therefore it is preferred that.These characteristics be for multilayer, thick film and Say effective characteristic.By the R in general formula (4) and (5)6When being set as 100mol%, if the polyether structure that general formula (1O) indicates is 1Omol% or more, then resin can get flexibility, low stress, with the plyability of substrate, therefore it is preferred that.In addition, from can get It is preferred when being 80mol% or less from the viewpoint of appropriate solution rate in developer solution.Further preferably 20mol%~ 50mol%.
For example, for the total amount 100mol% of general formula (4) and the repetitive unit of (5), R6Two are come from 70mol% The organic group of amine (diamines includes to have the organic group of polyether structure) and has aromatic ring with 30mol% Bivalent organic group when, be calculated as having 70mol% from diamines, (diamines includes the organic group for having polyether structure Group) organic group.At this point, R6In from diamines, (diamines includes the organic group for having polyether structure there are two above Group) organic group when, be calculated as 70mol%.
In addition, being used as general formula (4) and the R of (5) by also containing the organic group with fluorine atom5, so as to be assigned to resin Repellency is given, from the exudation of film surface when can inhibit alkali development, therefore it is preferred that.By inhibiting the exudation from film surface, so as to Obtain that unexposed portion is inviscid, nonvisualization residue, high residual film ratio resin film on processing graphic pattern.These characteristics are thick for realizing It is important characteristic for film processing.By R5Total amount when being set as 100mol%, if the organic group with fluorine atom is 20mol% or more then can get the anti-exudation effect at interface, can get when being 90mol% or less appropriate molten in developer solution Speed is solved, is preferred, further preferably 40mol%~60mol% from this viewpoint.
As the compound with fluorine atom, specifically, bis- (3, the 4- dicarboxyphenyi) hexafluoropropane dianhydrides of 2,2- can be enumerated Or the virtues such as compound and the acid dianhydride with amide groups obtained from replacing their aromatic ring alkyl, halogen atom Fragrant race's acid dianhydride etc..(A2) resin is preferably the resin for including the structure from these compounds.
By within the above range using the acid dianhydride of the alicyclic structure above-mentioned for being 4~40 with carbon atom number, with carbon original The diamines of the polyether structure of subnumber 20~100 and compound with fluorine atom, to can be obtained elongation is high and stress is low, And the high high sensitive photosensitive film of inviscid, nonvisualization residue residual film ratio in development.
The cloth again for the semiconductor devices that these characteristics are used in the laminated multi-layer in the form of the interlayer dielectric between metal line It is particularly useful in line purposes, noise filter purposes of inductor arrangement etc..In addition, the photosensitive film of the present invention can not make Afore-mentioned characteristics contain the structure from other acid dianhydrides, diamines other than acid dianhydride above-mentioned, diamines in the range of reducing.
As other acid dianhydrides, specifically, pyromellitic acid anhydride, 3 can be enumerated, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2, 3,3 ', 4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, Bis- (3, the 4- dicarboxyphenyi) propane dianhydrides of 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 2,2-, bis- (2, the 3- dicarboxyls of 2,2- Phenyl) propane dianhydride, bis- (3,4- dicarboxyphenyi) the ethane dianhydrides of 1,1-, bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of 1,1-, Bis- (3,4- dicarboxyphenyi) methane dianhydrides, bis- (2,3- dicarboxyphenyi) methane dianhydrides, 1,2,5,6- naphthalenetetracarbacidic acidic dianhydrides, 2, 3,6,7- naphthalenetetracarbacidic acidic dianhydrides, 2,3,5,6- pyridine tetracarboxylic acid dianhydrides, 3,4,9,10- tetracarboxylic acid dianhydrides, bis- (3,4- dicarboxyls Phenyl) aromatic tetracarboxylics dianhydride or the hydrogen by these compounds such as sulfone dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydrides Compound, 5- (2,5- dioxotetrahydrofuryl) -3- methyl -3- hexamethylenes obtained from atom alkyl, halogen atom substitution Alkene -1,2- diformazan acid dianhydride, 2,3,5- tri- carboxyl -2- cyclopentaneacetic acids dianhydrides, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetra- Formic acid dianhydride, 2,3,4,5- tetrahydrofuran tetracarboxylic acid dianhydrides, 3,5,6- tri- carboxyl -2- norbornane acetic acid dianhydrides, 3,4- dicarboxyls Base -1,2, ester ring type as 3,4- tetrahydrochysene -1- naphthalene succinic dianhydrides, half ester ring type tetracarboxylic acid dianhydride or by these compounds Compound and the acid dianhydride etc. with amide groups obtained from hydrogen atom alkyl, halogen atom substitution.These can with containing Carbon atom number combines two or more use for the acid dianhydride of 4~40 alicyclic structure.
As other diamines, specifically, bis- (3- amino-4-hydroxylphenyls) hexafluoropropane, bis- (3- amino -4- hydroxyls can be enumerated Base phenyl) sulfone, bis- (3- amino-4-hydroxylphenyls) propane, bis- (3- amino-4-hydroxylphenyls) methylenes, bis- (3- amino -4- hydroxyls Base phenyl) diamines containing hydroxyl, the 3- sulphurs such as ether, bis- (3- amino-4-hydroxies) biphenyl, bis- (3- amino-4-hydroxylphenyls) fluorenes Diamines containing mercapto, 3 such as the diamines containing sulfonic acid, the thioresorcin diamines such as sour -4,4 '-diamino-diphenyl ethers, 4 '-two Aminodiphenyl base ether, 4,4 '-diamino-diphenyl ethers, 3,4 '-diaminodiphenyl-methanes, 4,4 '-diaminodiphenyl-methanes, 3,4 '-diamino diphenyl sulfones, 4,4 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfides, 4,4 '-diamino hexichol Bis- (4- amino-benzene oxygens) benzene of base thioether, Isosorbide-5-Nitrae-, benzidine, m-phenylene diamine (MPD), p-phenylenediamine, 1,5- naphthylenediamines, 2,6- naphthylenediamines, Bis- (4- aminophenoxy phenyls) sulfones, bis- (3- aminophenoxy phenyls) sulfones, bis- (4- amino-benzene oxygens) biphenyl, bis- { 4- (4- ammonia Phenoxyl) phenyl ether, bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae -, 2,2 '-dimethyl -4,4 '-benzidines, 2,2 '-diethyls 4,4 '-benzidine of base -, 3,3 '-dimethyl -4,4 '-benzidines, 3,3 '-diethyl -4,4 '-benzidines, 2, 2 ', 3,3 '-tetramethyl -4,4 '-benzidines, 3,3 ', 4,4 '-tetramethyl -4,4 '-benzidines, 2,2 '-bis- (trifluoros Methyl) -4, the aromatic diamines such as 4 '-benzidines, a part of hydrogen atom carbon atom number 1~10 by these aromatic rings The substitutions such as alkyl, fluoroalkyl, halogen atom obtained from the ester ring types two such as compound, cyclohexanediamine, methylenebiscyclohexylamine Amine etc..These diamines can be used directly, or with corresponding diisocyanate cpd, trimethylsilylation diamines Form uses.Furthermore it is possible to combine the two or more diamine components in these and use.
In these, 3,4 '-diamino-diphenyl ethers, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino hexichol are preferably enumerated Base sulfone, 4,4 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfides, 4,4 '-diamino diphenyl sulfides, bis- (4- ammonia Phenoxyl phenyl) sulfone, bis- (3- aminophenoxy phenyls) sulfones, bis- (4- amino-benzene oxygens) biphenyl, bis- { 4- (4- aminobenzene oxygen Base) phenyl ether, bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae-, bis- (4- amino-benzene oxygens) benzene of 1,3-, bis- [4- (the 4- aminobenzene oxygen of 2,2- Base) phenyl] hexafluoropropane, bis- [4- (4- amino-benzene oxygens) phenyl] propane of 2,2-, 2,2- bis- (3- amino-4-hydroxylphenyls) six Fluoro-propane or compound obtained from replacing their aromatic ring alkyl, halogen atom and with the diamines of amide groups Deng.These can be two or more alone or in combination and use.
Furthermore it is possible to do not make heat resistance reduce in the range of import with siloxane structure aliphatic group, can be improved with The cementability of substrate.Specifically, as diamine component, can enumerate bis- (3- aminopropyls) tetramethyl disiloxanes, bis- (right Aminophenyl) prestox five siloxanes etc. with relative to the R in 100mol% general formulas (4) and (5)6For for 1~15mol% Substance etc. obtained from amount is copolymerized.
The use for requiring heat resistance on the way, preferably with the amount of the 50mol% or more of diamines entirety use aromatic diamine.
In addition, (A2) resin preferably has phenolic hydroxyl ingredient.In general formula (4) and (5), preferably R5、R6At least one of be Organic group with phenolic hydroxyl.By the way that there are phenolic hydroxyls, to can get the dissolving of the appropriateness in alkaline-based developer Property, and interact with emulsion and inhibit the dissolubility in unexposed portion, therefore residual film ratio can be made to improve, it realizes high sensitive Degree.In addition, phenolic hydroxyl also contributes to react with crosslinking agent, therefore from the sight that obtains high mechanical property, chemical resistance Point considers to be also preferred.
As the compound with phenolic hydroxyl, specifically, bis- (3, the 4- dicarboxyphenyi) hexafluoropropane two of 2,2- can be enumerated Acid anhydride or the fragrance such as compound and the acid dianhydride with amide groups obtained from replacing its aromatic ring alkyl, halogen atom Race's acid dianhydride, bis- (3- amino-4-hydroxylphenyls) hexafluoropropane, bis- (3- amino-4-hydroxylphenyls) sulfones, bis- (3- amino -4- hydroxyls Base phenyl) propane, bis- (3- amino-4-hydroxylphenyls) methylenes, bis- (3- amino-4-hydroxylphenyls) ethers, bis- (3- amino -4- hydroxyls Base) diamines of hydroxyls, a part of hydrogen atom by their aromatic ring such as biphenyl, bis- (3- amino-4-hydroxylphenyls) fluorenes Compound etc. obtained from the substitutions such as alkyl, fluoroalkyl, halogen atom with carbon atom number 1~10.(A2) resin preferably wraps Resin containing the structure from these compounds.
In general formula (4) and (5), n1And n2Indicate the degree of polymerization.The molecular weight of general formula (4) and the per unit of (5) is set as M, by alkali When the weight average molecular weight of soluble resin is set as Mw, polymerization degree n is found out with the formula of n=Mw/M.The Weight-average molecular of alkali soluble resins Amount is found out as being recorded embodiment by GPC (gel permeation chromatography).n1And n2It can be by using gel permeation chromatography (GPC), light scattering method, low-angle scattering of X-rays method etc. are measured easily to calculate to weight average molecular weight (Mw).It will repeat When the molecular weight of unit is set as M, the weight average molecular weight of polymer is set as Mw, n=Mw/M.Repeat number n in the present invention refers to, The value for being measured and being calculated using the most easy GPC (gel permeation chromatography) based on polystyrene conversion.
Using gel permeation chromatography in terms of polystyrene conversion, the weight average molecular weight of (A2) resin preferably 3,000~80, In the range of 000, more preferably in the range of 8,000~50,000.When within the scope of this, it is able to easily form thick film.
In addition, (A2) resin can utilize the end-capping reagents such as monoamine, acid anhydrides, acyl chlorides, monocarboxylic acid by end-capped.By by the end of resin End is blocked with the end-capping reagent with hydroxyl, carboxyl, sulfonic group, mercapto, vinyl, acetenyl or allyl, so as to It is enough to easily adjust solution rate of the resin in alkaline aqueous solution to preferred scope.End-capping reagent is preferably with respect to the complete of resin It is used with the amount of 0.1~60mol% for portion's amine component, more preferably 5~50mol%.
As end-capping reagent, specifically, in addition to 3- aminophenylacetylenes, 4- aminophenylacetylenes, 3,5- diacetylene anilines etc. Monoamine, 3- acetylenylbenzenes formic acid, 4- acetylenylbenzenes formic acid, 3,4- diacetylenes benzoic acid, 3,5- diacetylene benzoic acid etc. are single The carboxyl of above-mentioned monocarboxylic acid is carried out chloride and obtained by the acid anhydrides such as carboxylic acid, maleic anhydride, 5- norbornene -2,3- dicarboxylic acid anhydrides One carboxyl of the omega-dicarboxylic acids such as maleic acid is carried out compound obtained from chloride, by single chloride by the compound that arrives Closing object and active ester compound etc. obtained from the reaction of N- hydroxyl -5- norbornene -2,3- dicarboximides has insatiable hunger Other than the end-capping reagent of key, 5- amino-8-hydroxyquinolines, 1- hydroxyl -7- amino naphthalenes, 1- hydroxyl -6- amino naphthalenes, 1- can be also enumerated Hydroxyl -5- amino naphthalenes, 1- hydroxyl -4- amino naphthalenes, 2- hydroxyl -7- amino naphthalenes, 2- hydroxyl -6- amino naphthalenes, 2- hydroxyl -5- amino Naphthalene, 1- carboxyl -7- amino naphthalenes, 1- carboxyl -6- amino naphthalenes, 1- carboxyl -5- amino naphthalenes, 2- carboxyl -7- amino naphthalenes, 2- carboxyls -6- Amino naphthalenes, 2- carboxyl -5- amino naphthalenes, 2- aminobenzoic acids, 3- aminobenzoic acids, 4-aminobenzoic acid, 4-ASA, 5- Aminosalicylic acid, 6- aminosalicylic acids, 2- aminobenzenesulfonic acids, 3- aminobenzenesulfonic acids, 4- aminobenzenesulfonic acids, 3- amino -4,6- bis- Hydroxy pyrimidine, Ortho-Aminophenol, 3- amino-phenols, 4-aminophenol, 2- aminothiophenols, 3- aminothiophenols, 4- aminobenzenes The acid anhydrides such as the monoamines such as thiophenol, phthalic anhydride, cyclohexane cyclohexanedimethanodibasic acid anhydride, 3- hydroxyl phthalic anhydrides, 3- carboxylic phenols, 4- Carboxylic phenol, 3- carboxyls benzenethiol, 4- carboxyls benzenethiol, 1- hydroxyl -7- carboxyls naphthalene, 1- hydroxyl -6- carboxyls naphthalene, 1- hydroxyls -5- Carboxyl naphthalene, 1- sulfydryl -7- carboxyls naphthalene, 1- sulfydryl -6- carboxyls naphthalene, 1- sulfydryl -5- carboxyls naphthalene, 3- carboxyls benzene sulfonic acid, 4- carboxyl benzene The monocarboxylic acids such as sulfonic acid class and their carboxyl carry out single chloride compounds, terephthalic acid (TPA), O-phthalic obtained from chloride The omega-dicarboxylic acids such as acid, cyclohexane cyclohexanedimethanodibasic, 1,5- dicarboxyls naphthalene, 1,6- dicarboxyls naphthalene, 1,7- dicarboxyls naphthalene, 2,6- dicarboxyl naphthalenes Only 1 carboxyl carry out single chloride compounds obtained from chloride, pass through single chloride compounds and N- hydroxybenzotriazoles Active ester compound obtained from reaction etc. does not have the end-capping reagent of unsaturated bond.Furthermore it is possible to which these are not had unsaturation The hydrogen bond of the end-capping reagent of key uses vinyl to replace and used as the end-capping reagent with unsaturated bond.
The resin of at least either in the structural unit indicated with general formula (4) and (5) can according to known polyimides and The manufacturing method of polyimide precursor is manufactured.For example, can enumerate:(I) there will be R5The tetracarboxylic acid dianhydride of base and have R6Base Diamine compound, the method reacted under cryogenic of single-amino compound as end-capping reagent;(II) by having R5The tetracarboxylic acid dianhydride of base and alcohol and obtain diester, then with R6The diamine compound of base, the mono amino as end-capping reagent Close the method that object is reacted in the presence of condensing agent;(III) by with R5The tetracarboxylic acid dianhydride of base and alcohol and obtain two Then remaining two carboxyls are carried out chloride, and with R by ester6The diamine compound of base, the mono amino as end-capping reagent The method for closing object reaction;Etc..
The resin being polymerize using the above method preferably put into a large amount of water, methanol/water mixed liquor etc. in, make its precipitation And filtration drying, to be detached.By the precipitation operation, the oligomer ingredient such as unreacted monomer, dimer, tripolymer It is removed, the membrane property after heat cure improves.In addition, for carrying out obtained from the imidizate of polyimide precursor, closed loop For polyimides, it can be synthesized using the method for known imidization reaction after obtaining above-mentioned polyimide precursor.
Hereinafter, the preference as (I), illustrates the example of the manufacturing method of polyimide precursor.First, there will be R6 The diamine compound of base is dissolved in polymer solvent.Slowly added into the solution substantially with diamine compound equimolar amounts , have R5The tetracarboxylic dianhydride of base.Using mechanical agitator, in -20~100 DEG C, be preferable over 10~50 DEG C of stirrings O.5~ 100 hours, more preferably stir 2~24 hours.In the case of using end-capping reagent, after adding tetracarboxylic acid dianhydride, in -20~100 DEG C, be preferable over 10~50 DEG C stir 0.1~24 hour, then can slowly add end-capping reagent, can also be added at one time makes it Reaction.
As long as polymer solvent can dissolve the tetracarboxylic acid dianhydride class and Diamines as starting monomer, type does not limit especially It is fixed.For example, the amides such as n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone, γ-can be enumerated The ring-type such as butyrolactone, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, Alpha-Methyl-gamma-butyrolacton esters, carbonic acid The phenols such as the glycols such as the carbonates such as ethyl, propylene carbonate, triethylene glycol, metacresol, paracresol, acetophenone, 1,3- Dimethyl-2-imidazolinone, sulfolane, dimethyl sulfoxide (DMSO) etc..
For polymer solvent, if relative to used in polymerisation tetracarboxylic acid dianhydride, diamine compound, as end-capping reagent Single-amino compound total 100 mass parts for be more than 100 mass parts, then can be in the feelings that raw material, resin is not precipitated It is reacted, when being 1900 below mass part, is rapidly reacted, therefore preferably, more preferably 150~950 mass under condition Part.
Then, the photosensitive film of the present invention is illustrated.The photosensitive film of the present invention has by containing (B) photoacid generator Photonasty.It is irradiated by light by generates acid, so that dissolving of the illumination part in alkaline aqueous solution that is, (B) photoacid generator has The increased characteristic of property.As (B) photoacid generator, there are quinone di-azido compound, sulfonium salt, phosphonium salts, diazol, salt compounded of iodine etc..This In a little, from by with (A1) have the alkali soluble resins, (A2) of structural unit that general formula (1) indicates include selected from polyimides, Polybenzoxazole, polyamidoimide, their precursor and one or more of their copolymer alkali soluble resins be used in combination And from the viewpoint of excellent dissolution inhibition effect is presented, preferably use quinone di-azido compound.
Quinone di-azido compound can be enumerated:Chemical combination obtained from the sulfonic acid of diazido quinone is bonded with ester bond with polyol Object;Compound obtained from the sulfonic acid of diazido quinone is bonded with sulphonyl amine key with multiamino compound;The sulphur of diazido quinone Compound obtained from acid is bonded with ester bond or sulphonyl amine key with polyhydroxy multiamino compound;The sulfonic acid of diazido quinone is with ester Compound etc. obtained from key and sulphonyl amine key are bonded with polyhydroxy multiamino compound.
These polyols, multiamino compound functional group can not exclusively be replaced by quinonediazide group, preferred function The whole 50mol% or more of group is replaced by quinonediazide group.It is substituted by 50mol% or more using what above-mentioned quinonediazide group carried out When, the dissolubility in alkaline-based developer will not become excessively high, can get the contrast with unexposed portion, can obtain desired Pattern.By using such quinone di-azido compound, the i lines for the mercury lamp as common ultraviolet light can be obtained (365nm), h lines (405nm), g lines (436nm) have photosensitive positive light sensitivity film.Such compound can individually make With can also mix two or more and use.In addition, by using two kinds of photoacid generators, exposure portion and unexposed portion can be obtained The ratio between the solution rate of bigger, the photosensitive film of high sensitive as a result can be obtained.
Polyol can enumerate Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、 BisRS-3P、BisP-OCHP、Methylene tris-FR-CR、BisRS-26X、DML-MBPC、DML-MBOC、DML-OCHP、 DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP、DML-MTrisPC、TriML-P、TriML-35XL、TML-B P、TML-HQ、TML-pp-BPF、TML-BPA、 TMOM-BP, HML-TPPHBA, HML-TPHAP (be above trade name, Honshu chemical industry (strain) system), BIR-OC, BIP-PC, BIR-PC、BIR-PTBP、BIR-PCHP、BIP-BIOC-F、4PC、BIR-BIPC-F、TEP-BIP-A、46DMOC、46DMOEP、 TM-BIP-A (being above trade name, the organic material of the rising sun industrial (strain) system), 2,6- dimethoxy-methyls -4-TBP, 2,6- Dimethoxy-methyl paracresol, 2,6- diacetoxy methyl paracresol, naphthols, tetrahydroxybenzophenone, gallicin, Bisphenol-A, bis-phenol E, methylene bis-phenol, BisP-AP (trade name, Honshu chemical industry (strain) system) etc., but it is not limited to these.
Multiamino compound can enumerate Isosorbide-5-Nitrae-phenylenediamine, 1,3- phenylenediamines, 4,4 '-diamino-diphenyl ethers, 4,4 '-diamino two Phenylmethane, 4,4 '-diamino diphenyl sulfones, 4,4 '-diamino diphenyl sulfides etc., but it is not limited to these.
In addition, polyhydroxy multiamino compound can enumerate bis- (3- amino-4-hydroxylphenyls) hexafluoropropane of 2,2-, 3,3 '-dihydroxies Base benzidine etc., but it is not limited to these.
In the present invention, for two nitrine of quinone, diazido naphthoquinones -5- sulfonyls, diazido naphthoquinones -4- sulfonyls It is preferable to use.Diazido naphthoquinones -4- sulfonyls ester compounds have in the i lines region of mercury lamp to be absorbed, and i line exposings are suitable for.Two The absorption of azido naphthoquinones -5- sulfonyl ester compounds extends to the g lines region of mercury lamp, is suitable for g line exposings.
In the present invention, diazido naphthoquinones -4- sulphonyl base ester, diazido naphthalene are preferably selected according to the wavelength difference of exposure Quinone -5- sulfonyl ester compounds.Alternatively, it is also possible to obtain in same molecule and used diazido naphthoquinones -4- sulfonyls and The diazido naphthoquinones sulfonyl ester compounds of diazido naphthoquinones -5- sulfonyls, can also be by diazido naphthoquinones -4- sulphonyl Base ester compound is mixed with diazido naphthoquinones -5- sulfonyl ester compounds and is used.
The molecular weight of the quinone di-azido compound of the present invention is preferably in the range of 300~3,000.Point of quinone di-azido compound When son amount is more than 5,000, the inabundant thermal decomposition of quinone di-azido compound in heat treatment later, it is thus possible to which generation obtains Film heat resistance reduce, mechanical property reduce, cementability reduce the problems such as.
The quinone di-azido compound used in the present invention is synthesized using following methods by specific oxybenzene compound.Such as it can enumerate The method for making diazido naphthoquinones -5- sulfonic acid chlorides be reacted in the presence of triethyl amine with oxybenzene compound.The conjunction of oxybenzene compound The method etc. for making α-(hydroxy phenyl) styrene derivatives be reacted with polyphenol compound can be enumerated under an acid catalysis at method.
It is excellent as the sour component moderately stabilized substance for making to be generated by exposure in (B) photoacid generator used in the present invention Select sulfonium salt, phosphonium salts or diazol.Since the photosensitive film of the present invention is used as permanent film, for ring when the residuals such as phosphorus It is undesirable for border, and it also requires considering the tone of film, therefore sulfonium salt is preferably used in these.As especially preferred Substance can enumerate triarylsulfonium salt, can inhibit the variation of the tone of film.
For 100 mass parts of total amount of (A1) resin and (A2) resin, the content of (B) photoacid generator is preferably 0.01~ 50 mass parts.Wherein, quinone di-azido compound is preferably in the range of 3~40 mass parts.In addition, selected from sulfonium salt, phosphonium salts, diazonium Compound in salt in terms of whole preferably in the range of 0.05~40 mass parts, the model more preferably in 0.1~30 mass parts In enclosing.Content by making (B) photoacid generator can realize high sensitive in the range.Can also it contain as needed quick Agent etc..
The photosensitive film of the present invention contains (C) thermal cross-linking agent.As (C) thermal cross-linking agent, it is however preferred to have the change of alkoxy methyl Close object, the compound that especially preferably general formula (11) indicates.
[chemical formula 8]
(in general formula (11), R66Indicate the organic group of one~ten valence.Multiple R67It respectively can be the same or different, indicate carbon The alkyl of atomicity 1~4.R indicates 1~5 integer.S indicates the integer of 1~1O.)
Heat cross-linking reaction occurs in 160 DEG C or more for alkoxy methyl.Therefore, friendship is generated in the process for making photosensitive film heat cure Connection reaction, can be obtained good pattern form.
In addition, for the quantity of alkoxy methyl, in order to improve crosslink density, preferably there are 2 or more, in addition, in order to Chemical resistance is improved, more preferably there are 4 or more.In addition, in order to which the size for reducing the pattern after heat cure is uneven, preferably It is used as (C) thermal cross-linking agent at least one compound for having 6 or more alkoxy methyls.
The compound that general formula (11) indicates plays when less than 160 DEG C (generating heat cross-linking reaction in the temperature) as hot plasticizer Function.Lamination is preferable over 150 DEG C of temperature below and carries out, thus it is speculated that since photosensitive layer is melted by heating at this time, the contact with substrate Area increases, therefore the adaptation of the two improves.
As the concrete example of (C) thermal cross-linking agent, compound below can be enumerated, but be not limited to these.In addition, two can be contained Kind the above compound.
[chemical formula 9]
[chemical formula 10]
In order to enable to cured film in crosslink density, chemical resistance and improve with the adaptation of substrate, relative to (A1) for resin with for 100 mass parts of total amount of (A2) resin, the content of (C) thermal cross-linking agent is preferably 1 mass parts or more, more excellent It is selected as 5 mass parts or more.In addition, in order to make mechanical property improve, preferably 70 is below mass part, more preferably 50 mass parts with Under.
In order to make the mechanical property of the cured film after heat treatment improve, the weight average molecular weight (Mw) of (C) thermal cross-linking agent is preferably 100 More than, more preferably 300 or more.In addition, in order to make plyability improve, preferably 2,500 hereinafter, more preferably 2,000 or less.
The photosensitive film of the present invention preferably comprises the thermal cross-linking agent of the structural unit indicated with the following general formula (12).By containing Above-mentioned crosslinking agent, so as to further increase elongation while maintaining heat resistance and plyability.
[chemical formula 11]
(in general formula (12), R69And R70Each independently represent hydrogen atom or methyl.R68For the alkylene with 2 or more carbon atom number The bivalent organic group of base, and be straight-chain, branched and ring-type.As R68, alkyl, naphthenic base, alcoxyl can be enumerated Base, alkylether radicals, aIkylsilyl groups, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, ethylene Base, heterocycle, they are combined obtained from group etc., can further have substituent group.)
Thermal cross-linking agent itself has the aromatic series base of soft alkylidene and rigidity, therefore has heat resistance and plyability, simultaneously Elongation can be improved.As crosslinking group, acrylic acid series group, methylol, alkoxy methyl, epoxy group can be enumerated, but not It is defined in these.Wherein, from reacting with the phenolic hydroxyl of (A1) resin and (A2) resin, the heat resistance of cured film can be improved Viewpoint and from the viewpoint of reacting with capable of not being dehydrated, preferably epoxy group.
The compound that general formula (12) indicates for example can enumerate following compound as an example, but be not limited to following structures.
[chemical formula 12]
(integer that n is 1~5 in formula, m are 1~20.)
In above structure, from the viewpoint of realizing that heat resistance and elongation improve simultaneously, preferably n is 1~2, m is 3~7.
In addition, for 100 mass parts of total amount of (A1) resin and (A2) resin, the compound of general formula (12) expression adds Dosage is preferably 2~35 mass parts, more preferably 5~25 mass parts.By making additive amount be 2 mass parts or more, can fully obtain The effect that improves of elongation can inhibit the susceptibility of photosensitive film before curing to drop additionally by below mass part for 35 It is low.
The photosensitive film of the present invention can contain (D) acrylate compounds as needed.In the present invention, so-called (D) acrylate Compound refers to the compound with acryloyl group or methylacryloyl.(D) there is simple function third in acrylate compounds Olefin(e) acid ester and polyfunctional acrylic ester.So-called monofunctional acrylate refers to that there are one acryloyl group and methylacryloyls for tool In at least either compound.For example, acrylate, methacrylate, acrylamide and methacryl can be enumerated Amine etc..In addition, so-called polyfunctional acrylic ester based compound, refers to having in more than two acryloyl groups and methylacryloyl At least either compound.
The photosensitive film of the present invention is heat-treated after pattern processing.In the case of being used as positive light sensitivity film, at this time Acrylate compounds carry out thermal polymerization to each other in acrylate compounds or are reacted with alkali soluble resins, are crosslinked, by The elongation of this cured film improves.In the case of being used as negative photosensitive resin film, exposure when being processed by pattern, third Olefin(e) acid ester carries out photopolymerization each other, thus forms network with alkali soluble resins.
In the case of for monofunctional acrylate compound, the solidification of the film brought by cross-linking reaction is not sufficiently carried out, elongation The improvement effect of rate is low, therefore preferably polyfunctional acrylic ester.
As the preference of (D) acrylate compounds, can enumerate the villages Xin Zhong chemical industry (strain) NK Ester series 1G processed, 2G、3G、4G、9G、14G、23G、BG、HD、NPG、9PG、701、BPE-100、BPE-200、BPE-500、BPE-1300、A-200、 A-400、A-600、A-HD、A-NPG、APG-200、APG-400、APG-700、A-BPE-4、701A、TMPT、A-TMPT、A- TMM-3, A-TMM-3L, A-TMMT, A-9300, ATM-4E, ATM-35E, ATM-4P, AD-TMP, AD-TMP-L, A-DPH etc..Separately Outside, can enumerate common prosperity society chemical (strain) Light Ester Series Ps -1M processed, P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1.6HX, 1.9ND, 1.10DC, G-101P, G-201P, DCP-M, BP-2EM, BP-4EM, BP-6EM, TMP etc..Separately Outside, can enumerate common prosperity society chemical (strain) system " Light Acrylate " (registered trademark) series 3EG-A, 4EG-A, 9EG-A, 14EG-A、TMGA-250、NP-A、MPD-A、1.6HX-A、BEPG-A、1.9ND-A、MOD-A、DCP-A、BP-4EA、BP-4PA、 BA-134, BP-10EA, HPP-A, TMP-A, TMP-3EO-A, TMP-6EO-3A, PE-3A, PE-4A, DPE-6A etc..In addition, can Enumerate common prosperity society chemical (strain) Epoxy Ester series 40EM, 70PA processed, 200PA, 80MFA, 3002M, 3002A, 3000M, 3000A etc..In addition, East Asia synthesis (strain) system " ARONIX " (registered trademark) series M-203, M-208, M-210, M- can be enumerated 211B、M-215、M-220、M-225、M-240、M-243、M-245、M-260、M-270、M-305、M-309、M-310、M-313、 M-315, M-320, M-325, M-350, M-360, M-402, M-408, M-450 etc..In addition, Japanese chemical drug (strain) system can be enumerated " KAYARAD " (registered trademark) series R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R-551, R-712、R-604、R-684、GPO-303、TMPTA、THE-330、TPA-320、TPA-330、PET-30、T-1420(T)、RP- 1040 etc..In addition, Nippon Yushi (Co., Ltd.) " BLEMMER " (registered trademark) series GMR-H, GAM, PDE-50, PDE- can be enumerated 100、PDE-150、PDE-200、PDE-400、PDE-600、PDE-1000、ADE-200、ADE-400、PDP-400、ADP-200、 ADP-400、PDT-650、ADT-250、PDBE-200、PDBE-250、PDBE-450、PDBE-1300、ADBE-200、ADBE- 250, ADBE-450 etc..In addition, MRC Unitec (strain) MBAA processed etc. can be enumerated.These two or more chemical combination can be contained Object.
In above-mentioned (D) acrylate compounds, preferred molecular weight is 100 or more and 2,000 acrylate compounds below.It is logical Cross make molecular weight be 100 or more, the cured film of high elongation rate can be obtained, by be 2,000 hereinafter, can obtain have appropriateness Alkali-solubility, the resin combination with the high-compatibility of alkali soluble resins.
In addition, in the present invention, it can contain in the range of not damaging the heat resistance of the cured film obtained using heat treatment and remove (A2) other alkali soluble resins outside resin.Specifically, can enumerate acrylic acid is copolymerized obtained from acroleic acid polymerization It the phenolic resin such as object, silicone resin, Novolac resins, Resol resins, polyhydroxystyrene resin and is led into them Enter resin obtained from the crosslinking groups such as methylol, alkoxy methyl, epoxy group, their copolymer etc..Such resin dissolving In tetramethylammonium hydroxide, choline, triethylamine, dimethyl aminopyridine, monoethanolamine, DEAE diethylaminoethanol, sodium hydroxide, In the aqueous solution of the alkali such as potassium hydroxide, sodium carbonate.By containing these alkali soluble resins, heat-resistant resin envelope can kept Adaptation, excellent susceptibility while assign the characteristic of each alkali soluble resins.
As other alkali soluble resins, from the viewpoint of susceptibility, preferred phenolic resin.Phenolic resin can utilize known side Phenols and aldehydes are carried out polycondensation and obtained by method.The two or more resins with phenolic hydroxyl can be combined and contained.
As the preference of above-mentioned phenols, phenol, o-cresol, metacresol, paracresol, 2,3- dimethlbenzenes, 2,5- bis- can be enumerated Cresols, 3,4-Xylenol, 3,5- dimethlbenzenes, 2,3,5-TEP, 3,4,5- pseudocuminols etc..Particularly preferably Phenol, metacresol, paracresol, 2,3- dimethlbenzenes, 2,5- dimethlbenzenes, 3,4-Xylenol, 3,5- dimethlbenzenes or 2,3, 5- pseudocuminols.These two or more phenols can be combined and used.Deliquescent viewpoint from alkaline-based developer is examined Consider, preferably metacresol, the further preferably combination of metacresol and paracresol.That is, as the resin with phenolic hydroxyl, preferably comprises and contain There are the cresols Novolac resins of metacresol residue or metacresol residue and paracresol residue.At this point, in cresols Novolac resins The molar ratio (metacresol residue/paracresol residue, m/p) of metacresol residue and paracresol residue be preferably 1.8 or more.For this When range, it is shown in the dissolubility of the appropriateness in alkaline-based developer, good susceptibility can be obtained.More preferably 4 or more.
In addition, the preference as above-mentioned aldehydes, can enumerate formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, chloroethene Aldehyde, salicylide etc..In these, particularly preferred formaldehyde.These two or more aldehydes can be combined and used.Relative to 1mol phenol For class, the usage amount of the aldehydes is preferably 0.6mol or more, more preferably 0.7mol or more.Additionally, it is preferred that for 3mol hereinafter, More preferably 1.5mol or less.
Usually using acidic catalyst in the polycondensation reaction of phenols and aldehydes.As the acidic catalyst, for example, can enumerate hydrochloric acid, Nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-methyl benzenesulfonic acid etc..For 1mol phenols, the use of these acidic catalysts Amount is usually 1 × 10-5~5 × 10-1mol.In polycondensation reaction, opened as reaction medium, but from initial reaction stage usually using water Begin in the case of becoming heterogeneous system, using hydrophilic solvent or liphophilic solvents as reaction medium.It is molten as hydrophily Agent, such as the alcohols such as methanol, ethyl alcohol, propyl alcohol, butanol, propylene glycol monomethyl ether can be enumerated;Tetrahydrofuran, dioxane etc. Ring-type ethers.As liphophilic solvents, the ketones such as methyl ethyl ketone, methylisobutylketone, 2-HEPTANONE can be enumerated.Relative to every 100 For mass parts reaction raw materials, the usage amount of these reaction mediums is usually 20~1,000 mass parts.
The reaction temperature of polycondensation can suitably be adjusted according to the reactivity of raw material, usually 10~200 DEG C.As the anti-of polycondensation Induction method can suitably use following methods:The method that phenols, aldehydes, acidic catalyst etc. are added together, and it is made to react;Or Person, the method that phenols, aldehydes etc. are added while with progress is reacted in the presence of acidic catalyst;Etc..Polycondensation After reaction, in order to the removings such as existing unreacting material, acidic catalyst, reaction medium in system are typically made Reaction temperature rises to 130~230 DEG C, under reduced pressure removes volatile ingredient, recycles the resin with phenolic hydroxyl.
In the present invention, the weight average molecular weight (hereinafter referred to as " Mw " in terms of polystyrene conversion of phenolic resin.) it is preferably 1,000 More than, more preferably 2,000 or more.Additionally, it is preferred that for 20,000 hereinafter, more preferably 10,000 or less.When in the range, Workability, the susceptibility when positive type photosensitive organic compound of the present invention is coated on base material is excellent.
About the content of other alkali soluble resins, for 100 mass parts of total amount of (A1) resin and (A2) resin, from quick From the viewpoint of sensitivity, more than preferably 1 mass parts, more than more preferably 5 mass parts.From mechanical property, the viewpoint of heat resistance Consider, preferably 70 is below mass part, and more preferably 50 is below mass part.
In the resin that the photosensitive film of the present invention includes, the resin of the structure containing general formula (4) and (5) expression is preferably 30 matter Measure % or more.
In addition, the purpose for the susceptibility for improving photosensitive film can become smaller as needed in the shrinking percentage after not making solidification There is in range containing (E) compound of phenolic hydroxyl.
(E) with phenolic hydroxyl compound can for example enumerate Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z、BisOCHP-Z、BisOCR-CP、BisP-MZ、BisP-EZ、Bis26X-CP、BisP-PZ、BisP-IPZ、 BisCR-IPZ、BisOCP-IPZ、BisOIPP-CP、Bis26X-IPZ、BisOTBP-CP、TekP-4HBPA(TetrakisP- DO-BPA)、TrisP-HAP、TrisP-PA、TrisP-SA、TrisOCR-PA、BisOFP-Z、BisRS-2P、BisPG-26X、 BisRS-3P、BisOC-OCHP、BisPC-OCHP、Bis25X-OCHP、Bis26X-OCHP、BisOCHP-OC、Bis236T- OCHP, Methylene tris-FR-CR, BisRS-26X, BisRS-OCHP, (be above trade name, Honshu chemical industry (strain) System), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP- A (being above trade name, the organic material of the rising sun industrial (strain) system).
Preferably (E) have phenolic hydroxyl compound can enumerate Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、 BisRS-3P、BisP-OCHP、Methylene tris-FR-CR、BisRS-26X、BIP-PC、BIR-PC、BIR-PTBP、BIR- BIPC-F etc..
Especially preferred (E) have phenolic hydroxyl compound be Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P,BisRS-3P,BIR-PC,BIR-PTBP,BIR-BIPC-F.The compound that there is phenolic hydroxyl by containing (E), It can obtain following photosensitive films:It is insoluble in alkaline-based developer before exposure, meanwhile, when exposure, is easy to be dissolved in alkaline-based developer In, therefore the film detraction caused by developing is few, and can develop in a short time.It is set relative to (A1) resin and (A2) For 100 mass parts of total amount of fat, it is preferably 1~50 mass parts that (E), which has the content of the compound of phenolic hydroxyl, further excellent It is selected in the range of 3~40 mass parts.
The photosensitive film of the present invention can contain (F) solvent.As (F) solvent, following solvents can be used alone or as a mixture:γ-fourth The ethers such as non-protonic solvent, tetrahydrofuran, dioxane, the propylene glycol monomethyl ether of lactone isopolarity, dipropylene glycol The two alkylene glycol dialkylether class such as dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, acetone, first The ketones such as base ethyl ketone, diisobutyl ketone, diacetone alcohol, n,N-Dimethylformamide, n,N-dimethylacetamide, 3- methoxyl group fourths The acetate esters such as yl acetate, ethylene glycol monomethyl ether acetate, ethyl acetate, propylene glycol monomethyl ether, lactic acid second The esters such as ester, toluene, dimethylbenzene etc. are aromatic hydrocarbon etc..Relative to 100 mass parts of total amount of (A1) resin and (A2) resin Speech, the content of (F) solvent is preferably 0.0001 mass parts or more, and preferably 50 is below mass part.
The photosensitive film of the present invention can contain (G) silane compound, and (G) silane compound can be used as raising and basal substrate Cementability bonding additives use.As the concrete example of (G) silane compound, N- phenylaminoethyl trimethoxies can be enumerated Silane, N- phenylaminoethyls triethoxysilane, N- phenyl amino propyls trimethoxy silane, three second of N- phenyl amino propyls Oxysilane, N- phenyl aminos butyl trimethoxy silane, N- phenyl amino butyl triethoxysilane, vinyl trimethoxy Silane, vinyltriethoxysilane, vinyl trichlorosilane, vinyl three ('beta '-methoxy ethyoxyl) silane, 3- methyl-props Alkene acryloxypropylethoxysilane trimethoxy silane, 3- acryloyloxypropyltrimethoxysilanes, to styryltrimethoxysilane, 3- methacryloxypropylmethyl dimethoxysilanes, 3- methacryloxypropyl methyl diethoxysilanes, tool There is the silane compound of structure as shown below, but is not limited to these.Containing two or more in them.
[chemical formula 13]
For 100 mass parts of total amount of (A1) resin and (A2) resin, the content of (G) silane compound is preferably 0.01 More than mass parts and 15 is below mass part.When within the scope of this, it can be obtained while keeping the heat resistance of positive light sensitivity film Obtain the sufficient effect as bonding additives.
In addition, for the purpose for the wetability for improving photosensitive film and substrate, ethyl lactate, propylene glycol monomethyl ether second can be contained The ethers such as the ketones such as the alcohols such as the esters such as acid esters, ethyl alcohol, cyclohexanone, methylisobutylketone, tetrahydrofuran, dioxane.Separately Outside, the powder etc. also containing the inorganic particulates such as silica, titanium dioxide or polyimides.
The photosensitive film of the present invention preferably comprises the compound (being recorded as (H) ingredient below) of (H) the following general formula (13) expression.It is logical Crossing significantly improves the film after lamination and the adaptation of metal material (especially copper) containing (H) ingredient.Its reason is general formula (13) S atom, N atoms of the compound indicated and metal surface interact, and then are to form and are easy to send out with metal covering The stereochemical structure of raw interaction.Based on these effects, photonasty can be assigned to resin combination, and even if with addition Also the resin cured film excellent in adhesion with metal material can be obtained in the composition of agent.In general formula (13), R71~R73Indicate O Any one of atom or S atom, N atoms, and R71~R73At least one of indicate S atom.R when 1 expression 0 or 1,1 is 071 Indicate oxygen atom or sulphur atom, 1 R when being 171Indicate nitrogen-atoms.M, n indicates 1 or 2.R74~R76Each independently represent hydrogen atom Or the organic group of carbon atom number 1~20.As R74~R76, hydrogen atom, alkyl, naphthenic base, alkoxy, alkyl ether can be enumerated Base, aIkylsilyl groups, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocycle, Group obtained from they are combined etc. can further have substituent group.
[chemical formula 14]
In addition, for 100 mass parts of total amount of (A1) resin and (A2) resin, the additive amount of (H) ingredient is preferably 0.1 ~10 mass parts.By making additive amount be 0.1 mass parts or more, it can fully obtain the adaptation after the lamination with metal material and carry High effect, additionally by below mass part for 10, when the photosensitive film used in the present invention is eurymeric, can inhibit by with sense The susceptibility of photosensitive film caused by the interaction of photo etching reduces, therefore it is preferred that.
In the compound that the general formula (13) used in the present invention indicates, it is preferred that R71~R73Indicate that O atom or S atom, N are former Any one of son, and R71~R73At least one of be S atom.Typically, in compound of the addition containing N atoms In the case of, due to the interaction of emulsion and the compound containing N atoms, susceptibility may be damaged, but by containing S originals Son can suitably keep repercussion effect, and the effect of adaptation raising can be obtained in the case where not making susceptibility reduce.Separately Outside, from the viewpoint of the adaptation after the lamination with the substrate other than the metals such as silicon, more preferably there is tri-alkoxy methyl.
The compound that general formula (13) indicates can enumerate compound below as an example, but be not limited to following structures.
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
The manufacturing method of the photosensitive film of the example present invention.Such as it can enumerate:(A1) had into the structural unit that general formula (1) indicates Alkali soluble resins, (A2) with selected from the substituent group reacted with above-mentioned (A1) alkali soluble resins, polyimides, polyphenyl Alkali soluble resins, the production of (B) light of Bing oxazoles, polyamidoimide, their precursor and one or more of their copolymer The flask of glass system, stainless steel is added in sour agent, (C) thermal cross-linking agent, (F) solvent and the other compositions that are added as needed on In container, make the method for its stirring and dissolving, the method made it dissolve using ultrasonic wave, using planetary using mechanical agitator etc. Churning deaerator makes method of its stirring and dissolving etc..Including (A1) resin, (A2) resin, (B) photoacid generator, (C) heat cross-linking The viscosity of the composition of agent, (F) solvent etc. is preferably 200~10,000mPas.In addition, in order to remove impurity, using hole Diameter size is that 0.1 μm~5 μm of filter is filtered.
The photosensitive film of the present invention preferably has support membrane.By will include (A1) resin, (A2) resin, (B) photoacid generator, (C) composition of thermal cross-linking agent, (F) solvent etc. is coated on support membrane, then it is dried, so as to obtain propping up Hold the photosensitive film with photosensitive layer on film.
Support membrane is not particularly limited, and polyethylene terephthalate (PET) film, polyphenylene sulfide film, polyimides can be used The usually commercially available various films such as film.In order to improve support membrane and photosensitive film joint surface adaptation and fissility, can implement The surface treatment of organosilicon, silane coupling agent, aluminum chelating agent, polyureas etc..In addition, the thickness of support membrane is not particularly limited, from From the viewpoint of workability, preferably in the range of 10~100 μm.
In addition, for the photosensitive film of the present invention, in order to protect surface, there can be protective film on film.Thereby, it is possible to Protect polluting for the polluters such as rubbish, dust of the photosensitive film surface not in by air.
As protective film, polyolefin film, polyester film etc. can be enumerated.The protective film preferably small film with the bonding force of photosensitive film.
As the composition coating that will include (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal cross-linking agent, (F) solvent etc. In on support membrane, formed photosensitive layer method, can enumerate and utilize flush coater, roll coater, silk-screen printing, doctor knife coater, die coating machine, pressure Prolong coating machine, meniscus coating machine, bar coater, roll coater, comma coating machine, gravure coater, silk screen coating machine, slot die The method of the progress such as machine.In addition, coating film thickness according to the difference of coating method, the solid component concentration of composition, viscosity etc. and Difference, typically, the film thickness of the photosensitive layer obtained after dry is preferably 0.5 μm or more and 100 μm or less.In addition, more preferably It is 3 μm or more and 40 μm or less.
Baking oven, heating plate, infrared ray etc. can be used in drying.As long as drying temperature and drying time can make solvent volatilize In range, preferably suitably set in the range of semiconductor becomes uncured or semi-cured state with resin membrane material It is fixed.Specifically, it is preferable that carrying out 1 minute to dozens of minutes in the range of from 40 DEG C to 120 DEG C.Furthermore it is possible to combine these temperature Degree carries out interim heating, can be heat-treated within 1 minute in such as 50 DEG C, 60 DEG C, 70 DEG C of each progress.
Then, it is illustrated for the method for using photosensitive film to manufacture semiconductor devices.When photosensitive film has protective film, It is removed first.Keep photosensitive film opposite with substrate, make its fitting using heating crimping, photosensitive film is transferred to substrate, It is laminated.Then, bearing film stripping is obtained into photonasty envelope.Heating, which crimps, can utilize hot-pressing processing, heat lamination to handle, The progress such as thermal vacuum lamination treatment.For the temperature being laminated for carrying out heating crimping, from adaptation, the embeddability with substrate From the viewpoint of, preferably 40 DEG C or more, more preferably 50 DEG C or more.In addition, in order to prevent heat crimp when photosensitive film Cure and the resolution ratio that the pattern in exposure imaging process formed made to be deteriorated, the temperature for heating crimping be preferably 150 DEG C hereinafter, More preferably 120 DEG C or less.In addition, in thermo-compression bonding, for the purpose for removing bubble, can carry out under reduced pressure.
In addition, after photosensitive film is laminated to substrate, the stripping of support membrane from photosensitive film is below at 0 DEG C or more 100 DEG C It is carried out in temperature range.
The substrate used can enumerate silicon wafer, ceramic-like, GaAs, organic system circuit board, inorganic system's circuit board and at this Substance etc. obtained from the constituent material of configuration circuit on a little substrates, but it is not limited to these.
As the example of organic system circuit board, it is copper-clad laminated that the glass baseplates such as glass cloth epoxy copper-clad laminated board can be enumerated Compound copper-clad laminated board, polyetherimide resin substrate, the polyether ketone resin bases such as plate, glass non-woven fabric epoxy copper-clad laminated board The flexibility base such as the heat-resisting thermoplasticity substrates such as plate, polysulfones system resin substrate, polyester copper membrane substrate, polyimide copper-clad ilm substrate Plate.In addition, the example of inorganic system's circuit board can enumerate the ceramic substrates such as aluminum oxide substrate, aluminium nitride substrate, silicon carbide substrate, The metal systems substrates such as aluminium base substrate, iron-based substrate.The example of the constituent material of circuit can be enumerated containing gold such as gold, silver, copper The conductor of category, the resistive element containing inorganic system's oxide etc., the low-dielectric containing glass based material, resin etc., containing resin, The high dielectric of high-dielectric constant inorganic particle etc., the insulator etc. containing glass based material etc..
Then, on the photonasty envelope formed using the above method, photochemical penetrate is irradiated by the mask with desired pattern Line is exposed.As the actinic ray used in exposure, there are ultraviolet light, luminous ray, electron ray, X-ray etc., but this It is preferable to use the i lines (365nm) of mercury lamp, h lines (405nm), g lines (436nm) in invention.In photosensitive film, support membrane relative to In the case that these light are transparent material, it can be exposed after photosensitive film stripping by support membrane, it can not also It removes and is exposed.In the case where not removing and be exposed, shell after exposure, before carrying out development treatment by support membrane From.
In order to form pattern, unexposed portion is removed using developer solution after exposure.As developer solution, preferably tetramethyl hydroxide The aqueous solution of ammonium, diethanol amine, DEAE diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, two Ethamine, methylamine, dimethylamine, dimethyl amino ethyl ester, dimethylaminoethanol, dimethylaminoethyl methacrylate, The aqueous solution of the compound of the display alkalinity such as cyclohexylamine, ethylenediamine, hexamethylene diamine.In addition, can be according to circumstances in these alkali Individually contain in property aqueous solution or combines a variety of and contain:N-methyl-2-pyrrolidone, n,N-Dimethylformamide, N, N- bis- The alcohol such as methylacetamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, dimethacrylamide isopolarity solvent, methanol, ethyl alcohol, isopropanol The ketones such as the esters such as class, ethyl lactate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, isobutyl ketone, methylisobutylketone Deng.
Development can be carried out by following methods:Above-mentioned developer solution is sparged on the face with photonasty envelope;It is impregnated in development In liquid;Apply ultrasonic wave while impregnating;Or spray development liquid on one side so that substrate is rotated while;Etc..Developing time, development As long as the condition in step as the temperature of developer solution when development is the condition that unexposed portion is removed, micro- in order to process Thin pattern removes residue between pattern, preferably further develops after removing unexposed portion.
Rinsing processing can be carried out after development with water.It herein, also can be by the alcohols such as ethyl alcohol, isopropanol, ethyl lactate, propylene glycol list first Esters such as base ether acetic acid ester etc., which are added to the water, carries out rinsing processing.The resolution ratio of pattern in development improves, development conditions In the case of permissible range is increased, the process for carrying out baking processing can be introduced before development.As the temperature, preferably 50~ In the range of 180 DEG C, especially more preferably in the range of 60~120 DEG C.Time is preferably 5 seconds~a few hours.
After forming pattern, applies the temperature from 120 DEG C to 400 DEG C and obtain cured film.The heat treatment is:Temperature is selected, Periodically heat up;Or certain temperature range is selected, it continuously heats up, implements 5 minutes to 5 hours on one side on one side.As an example, It is heat-treated within 30 minutes in 130 DEG C, 200 DEG C of each progress.Alternatively, can enumerate through 2 hours from room temperature ramped thermal to 250 DEG C of grade sides Method.At this point, heating temperature is preferably 150 DEG C or more and 300 DEG C of temperature below, further preferably 180 DEG C or more and 250 DEG C Below.
In order to improve insulating properties, the film thickness of cured film is preferably 0.5 μm or more, more preferably 2 μm or more.In addition, from reduce by From the viewpoint of the warpage for the substrate that residual stress is brought, preferably 100 μm hereinafter, more preferably 40 μm or less.
Cured film made of the photosensitive film of the present invention is cured can be suitably used for the passivating film of semiconductor, semiconductor is protected The purposes such as insulating layer of cuticula, the interlayer dielectric of high-density installation multilayer wiring, organic electroluminescent device.In addition, will Cured film made of the photosensitive film of the present invention is cured can be used in the state of forming the embossed pattern layer of the cured film Semiconductor devices.
Alternatively, it is also possible to which cured film to be configured at 2~40 μm of film thickness on substrate as described above, and copper cloth is configured on it Then line further forms cured film as the insulating film between thin copper film, to make semiconductor using 2~40 μm of film thickness Device.
The preferred structure of semiconductor devices configured with cured film made of being cured the photosensitive film of the present invention is illustrated in In following figure 1.Passivating film 2 is formed on semiconductor element 1.The photosensitive film of the present invention is laminated to passivation using heating crimping It on film 2, is thermally dried using heating plate etc., the pattern of photonasty envelope is formed by exposure imaging.It is formed photosensitive Property envelope pattern after, cured in high-temperature processing technology, formed cured film 3.Using sputtering, vapor deposition, electroless plating, The methods of electrolytic coating forms metal line in cured film 3.In turn, it in order to protect metal line, is crimped using heating and incite somebody to action this The photosensitive film of invention is laminated, and is thermally dried using heating plate etc., and pattern is formed by exposure imaging.It is formed After the pattern of photonasty envelope, cured in high-temperature processing technology, forms cured film 5.It is formed and is cured using the above method Film, it is with high adaptation, flat with high adaptation and cured film and metal line each other thus, it is possible to provide cured film The high semiconductor devices of smooth property.
Then, illustrated configured with cured film, inductor made of being cured the photosensitive film of the present invention using attached drawing The application examples of the coil component of device.Fig. 2 is the sectional view of the coil component of the cured film with the present invention.As shown in Fig. 2, It is formed with insulating film 7 on substrate 6, and forms cured film 8 in a pattern on insulating film 7.As substrate 6, iron oxygen is used Body etc..The photosensitive film of the present invention can be used for the arbitrary film in cured film 7 and cured film 8.It is formed in the opening portion of the pattern Metal film 9 (Cr, Ti etc.), and plating is formed with metal line 10 (Ag, Cu etc.) on metal film 9.Metal line 10 (Ag, Cu Deng) be formed as helical form.By repeat multiple 7~10 process and be laminated, so as to make it have as line The function of circle.Finally, metal line 10 (Ag, Cu etc.) is connect by metal line 11 (Ag, Cu etc.) with electrode 12, passes through sealing Resin 13 and sealed.
Then, using description of the drawings configured with by the present invention photosensitive film cured made of cured film, have it is hollow The electronic unit in portion or the application examples of semiconductor devices.Fig. 3 is in the acoustic wave device for used the photosensitive film of the present invention An example of the sectional view in empty portion.As shown in figure 3, being formed in substrate 14:By with more electrode fingers being respectively inserted into mutually IDT (Inter Digital Transducer, interdigital transducer) electrode 15 that a pair of of comb-type electrode is constituted;With for obtaining The landing pad 16 conducted.Herein, substrate 14 can for example enumerate lithium niobate, potassium niobate, lithium tantalate, crystal, barium silicate (1angasite), ZnO, PZT, lithium tetraborate etc..As electrode 15 and the material of landing pad, for example, can enumerate A1, Pt, Cu, The metals such as Au, Ti, Ni, Cr, W, Pd, Co, Mn.In addition, forming photonasty to ensure hollow portion 17 on piezoelectric substrate 14 The embossed pattern layer of the cured film of resin combination is as Zhi Chengcai 18.As photosensitive polymer combination, such as can enumerate poly- Imide series resin, epoxy system resin, acrylic resin, phenol resin etc..It is arranged on substrate 15 via Zhi Chengcai 17 There is coated material 19 to cover electrode 15.Herein, photosensitive film of the invention is used for coated material 19, it can also be used to Zhi Chengcai 17.Quilt The thickness for covering material 19 is, for example, 20 μm.Protection component 20 is set in a manner of covering substrate 14, Zhi Chengcai 18 and coated material 19. Thickness for instance in the protection component 20 on coated material 19 is, for example, 30 μm.Protection component is insulating materials, such as can be enumerated Epoxy system resin, benzocyclobutane olefine resin, silicon system resin, SOG (Spin On Grass, spin-on glasses layer) etc..It can support The inside of material 17 and coated material 19 is provided with via conductor 21 in a manner of penetrating through in a thickness direction.Connect on via conductor 21 It connects and is formed with solder projection 22.
Then, using attached drawing come illustrate to have used the present invention photosensitive film, in the semiconductor for including the substrate with layer difference Application examples in device.Fig. 4 is the amplification sectional view of the pad portion of the semiconductor devices of the cured film with the present invention, is quilt The referred to as structure of fan-out wafer grade encapsulation (being fanned out to WLP).Be formed with A1 pads 24, passivating film 25 silicon wafer 23 after cutting and by It is cut into each chip, is then sealed using resin 26.When being sealed, heated, due to the contraction of resin 26 And it is poor that (T-1) layer is generated between chip 23 and resin 26.At this point, by 26 table of (S-1) upper layer part and resin on 23 surface of chip (T-1) layer difference that (S-2) lower layer part in face is formed is 2~40 μm.On each (S-1) upper layer part and (S-2) lower layer part are entire Cured film 27 is formed in the form of the pattern of the photosensitive film of the present invention, is configured at cured film on (S-1) upper layer part and is matched (T-2) the layer difference for being placed in the cured film on above-mentioned (S-2) lower layer part is 5 μm or less.
In turn, metal (Cr, Ti etc.) film 28, metal line 29 are formed.Then, exhausted on the sealing resin being formed in outside chip The opening portion of velum 30 forms barrier metal 31 and solder projection 32.It is following semiconductor packages to be fanned out to WLP:By using epoxy Expansion is arranged on the periphery of semiconductor chip, from the electrode of semiconductor core on piece up to the extension in the sealing resins such as resin Part implements to connect up again, and also carries soldered ball in expansion and ensure that necessary number of terminals.In being fanned out to WLP, with across The mode that boundary line is more formed by by the interarea of the interarea of semiconductor chip and sealing resin is provided with wiring.That is, comprising It implements and forms interlayer dielectric on the base material of the material of the semiconductor chip and sealing resin of metal line more than both, and Wiring is formed on the interlayer dielectric.In addition to this, it is formed by be embedded in recess portion in glass epoxy substrate and partly lead In the semiconductor packages of the type of body chip, to cross over the side of the boundary line of the interarea of semiconductor chip and the interarea of printed base plate Formula setting wiring.In this embodiment, interlayer dielectric is also formed on the base material comprising two or more materials, and at this Wiring is formed on interlayer dielectric.Cured film is configured at comprising two or more made of the photosensitive film of the present invention is cured Material substrate on when, can reduce that layer present on substrate is poor, maintain the flatness of cured film, therefore can suitably serve as The interlayer dielectric being arranged on the base material comprising two or more materials.
Embodiment
Hereinafter, enumerating embodiment and comparative example, the present invention will be described, but the present invention is not limited by them.The quinone of synthesis The evaluation of the esterification yield of two azido compounds, the evaluation of photosensitive film carry out by the following method.
<The assay method of film thickness>
For the film after prebake conditions and after development, (strain) Lambda STM-602 processed are manufactured using Dainippon Screen, with Polyimides is measured as benchmark with refractive index 1.629.
<The measurement of the acid imide rate of polyimides>
For the acid imide rate of (A2) alkali soluble resins, using spin-coating method by the solid component concentration of polyimide resin For 50 mass % N-Methyl pyrrolidone (being denoted as NMP below) solution coating on 6 inches of silicon wafer, then use 120 DEG C heating plate (Dainippon Screen manufacture (strain) SKW-636 processed) toast within 3 minutes, makings thickness is 10 μm of ± 1 μ The prebake conditions film of m.The film is split into two halves, half therein is put into inert gas baking oven (Koyo Thermo Systems systems INH-21CD in), the solidification temperature for rising to 350 DEG C through 30 minutes carries out heating for 60 minutes in 350 DEG C.Then, slowly Being cooled in baking oven becomes 50 DEG C hereinafter, obtaining cured film.For obtained cured film (A) and film before curing (B), Fu is used In leaf transformation infrared spectrophotometer FT-720 (hole field make made) measure infrared absorption spectrum.It finds out from imide ring The 1377cm of C-N stretching vibrations-1Neighbouring peak intensity, by " peak intensity of peak intensity/cured film (A) of film (B) before curing " Value as acid imide rate.
<The evaluation of plyability>
By the protection film stripping of the photosensitive film made in aftermentioned each Examples and Comparative Examples.Then, release surface is laminated to On silicon wafer or on copper base.Copper base uses the substrate (copper plated substrate) for having following metal material layers on surface, described Metal material layer is titanium, the copper for sputtering 100nm on silicon, then electrolytic coating is utilized to form copper plating with 2 μm of thickness Obtained from film.Lamination uses laminater ((strain) Takatori systems, VTM-200M), is 80 DEG C, roller temperature in operating temperature It is carried out under conditions of degree is 80 DEG C, vacuum degree 150Pa, labeling rates are 5mm/ seconds, application pressing force is 0.2Mpa.After lamination, The center of film on substrate, using cutting guide rail by be in 2mm × 2mm interval formation 100 it is square in a manner of with chessboard Trellis engraves indentation on photonasty envelope.After tessellated bonding partially adhesive tape, opposing substrate is along 90 ° of angle Direction is stretched, and is carried out stripping and is taken off.Carry out stripping take off after, the quantity of the photonasty envelope to being removed in 100 is counted Number.It when the quantity of stripping is few, indicates that adaptation is high, indicates that adaptation is low when more.Preferably 50 hereinafter, more preferably 20 hereinafter, Further preferably 10 or less.The case where evaluation that will carry out plyability on silicon, will be enterprising in copper base as condition 1 The case where evaluation of row plyability, is as condition 2.
<The evaluation of pattern processability (high sensitive)>
By the protection film stripping of the photosensitive film made in each Examples and Comparative Examples, laminater ((strain) Takatori is used System, VTM-200M), operating temperature is 80 DEG C, roll temperature is 120 DEG C, vacuum degree 150Pa, labeling rates are 5mm/ seconds, The release surface is laminated on 8 inch silicon wafers by application pressing force under conditions of being 0.2Mpa.Then, using 120 DEG C of heating plate (using ACT-8) toast within 3 minutes, makes the prebake conditions film that thickness is 10 μm.Use i line stepping exposure devices (NIKON NSRi9), with 0~1000mJ/cm2Light exposure with 10mJ/cm2Step pitch the film is exposed.After exposure, with 2.38 matter Tetramethylammonium hydroxide (TMAH) aqueous solution (Mitsubishi Gas Chemical (strain) systems, ELM-D) for measuring % carries out 90 seconds Development, is then rinsed with pure water, and the development film A with 5 μm of solitary diastema (isolated aperture) is obtained.
For development film A, will it is exposed and developed after 5 μm solitary diastema exposed portion completely dissolve out and disappear light exposure (being known as minimum exposure amount Eth) is used as susceptibility.Eth is 400mJ/cm2When following, it can determine whether as high sensitive.More preferably 300mJ/cm2Hereinafter, further preferably 250mJ/cm2Below.
<The forthright evaluation of high drawing>
By the protection film stripping of the photosensitive film made in each Examples and Comparative Examples, laminater ((strain) Takatori is used System, VTM-200M), operating temperature is 80 DEG C, roll temperature is 120 DEG C, vacuum degree 150Pa, labeling rates are 5mm/ seconds, Under conditions of application pressing force is 0.2Mpa, it is laminated on silicon wafer in a manner of T1=11 μm of film thickness.With heating plate by layer Then substrate after pressure used inert gas baking oven CLH-21CD-S (Koyo Thermo in 120 DEG C of prebake conditions 3 minutes Systems (strain) makes), under nitrogen flowing, 220 are warming up to 3.5 DEG C of heating rate per minute with 20ppm oxygen concentrations below DEG C, it carries out heating for 1 hour in 220 DEG C.It is removed with the hydrofluoric acid aqueous solution of 46 mass %, it is (heat-resisting to obtain cured film Property resin film).The cured film obtained by this method is cut into 7 × 1cm with single-blade, with Tensilon universal testing machines (Orientec Corporation systems, RTM-100) stretched it with 50mm/ minutes.It finds out and removes amount of tension at this time To be worth obtained from sample length.The measurement is carried out for 10 samples, using its maximum value as elongation.Elongation is preferably 10% or more, more preferably 20% or more, further preferably 40% or more.
<5% weight reduces temperature measuring (evaluation of heat resistance)>
Using thermogravimetric reduce measuring machine (Shimadzu Seisakusho Ltd. TGA50), will utilize with it is above-mentioned<The forthright evaluation of high drawing>It is identical The obtained cured film of method under nitrogen flowing, under the conditions of 80mL/min, heated up and carried out with the speed of 10 DEG C/min It measures.It is preferably 260 DEG C or more that 5% weight, which reduces temperature, more preferably 300 DEG C or more, further preferably 340 DEG C or more.
The abbreviation of the compound used in each Examples and Comparative Examples and its title are as described below.
PMDA-HH:1S, 2S, 4R, 5R- cyclohexanetetracarboxylic acid dianhydride
TDA-100:3,4- dicarboxyls -1,2,3,4- tetrahydrochysene -1- naphthalene amber acid dianhydrides
CBDA:Cyclobutanetetracarboxylic dianhydride
6FDA:4,4 '-hexafluoroisopropylidenyl, two O-phthalic acid dianhydride
ODPA:3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydrides
SiDA:Bis- (3- aminopropyls) disiloxane of 1,1,3,3- tetramethyl -1,3-
BAHF:2,2- bis- (3- amino-4-hydroxylphenyls) hexafluoropropane
DAE:4,4 '-diamino-diphenyl ethers
NMP:N-methyl-2-pyrrolidone
ED-600:JEFFAMINE ED-600 (trade name, HUNTSMAN (strain) systems)
MAP:M-aminophenol
NA:5- norbornene -2,3- dicarboxylic acid anhydrides
KBM-403:3- glycidoxypropyltrime,hoxysilanes (silane compound (a)).
(C) thermal cross-linking agent for being used in each embodiment, comparative example, (H) compound are for example following shown.
[chemical formula 20]
[chemical formula 21]
The synthesis of 1 quinone di-azido compound (a) of synthesis example
Under drying nitrogen stream, TrisP-PA (trade name, Honshu chemical industry (strain) system) 21.22g (0.05mol), two are folded Nitrogen base naphthoquinones -5- sulfonic acid chlorides 26.86g (0.10mol), diazido naphthoquinones -4- sulfonic acid chlorides 13.43g (0.05mol) are dissolved in 1, In 4- dioxanes 50g, and it is made to be room temperature.Confirmed on one side so that in system not become 35 DEG C or more, on one side to Wherein be added dropwise with the mixed triethylamine 15.18g of Isosorbide-5-Nitrae-dioxane 50g.It is stirred 2 hours in 30 DEG C after dropwise addition.It will Triethylamine salt filters, and filtrate is put into water.Then, the precipitation of precipitation is collected by filtering.Pass through vacuum drier pair The precipitation is dried, and obtains the quinone di-azido compound (a) of following formula expression.
[chemical formula 22]
The synthesis of 2 polyhydroxystyrene resin of synthesis example (a0-1)
Have in tetrahydrofuran 500ml, the mixed solution as the s-butyl lithium 0.01mol of initiator to addition, addition with mole Ratio than 3: 1 add up to 20g to t-butoxystyrene and styrene, make its polymerization while stirring 3 hours.Polymerization stops Only reaction adds methanol 0.1mol into reaction solution to carry out.Then, in order to by polymer purification, by reaction mixture It injects in methanol, the polymer after sedimentation is dried, white polymer is as a result obtained.In turn, it is dissolved in acetone 400ml, in 60 DEG C are added a small amount of concentrated hydrochloric acid and stir 7 hours, are then injected into water, polymer is made to precipitate, will be to t-butoxystyrene It is deprotected and is converted into hydroxy styrenes, carry out washing drying, as a result obtain purified 4-Vinyl phenol and styrene Copolymer (is denoted as (a0-1)) below.In addition, by using the analysis that GPC is carried out, weight average molecular weight (Mw) is that 3500 (GPC is poly- Styrene converts), dispersion degree is (Mw/Mn) 2.80.
The synthesis of 3 polyhydroxystyrene resin of synthesis example (a0-2)
In addition to replacing between t-butoxystyrene and use other than t-butoxystyrene of above-mentioned synthesis example 2, similarly into Row operation.Between obtain for the copolymer (being denoted as below (a0-2)) of hydroxy styrenes and styrene, by using GPC The analysis of progress, weight average molecular weight (Mw) are 5000 (conversions of GPC polystyrene), and dispersion degree is (Mw/Mn) 3.20.
The synthesis of 4 polyhydroxystyrene resin of synthesis example (a0-3)
Other than being added without the styrene of above-mentioned synthesis example 2, it is carried out similarly operation.For obtained 4-Vinyl phenol tree For fat (being denoted as below (a0-3)), by using the analysis that GPC is carried out, weight average molecular weight (Mw) is 3000 (GPC polystyrene Conversion), dispersion degree is (Mw/Mn) 1.60.
The synthesis of 5 alkali soluble resins of synthesis example (a1-1)
Make polyhydroxystyrene resin (a0-1) be dissolved in sodium hydroxide 80g (2.0mol) is dissolved in obtained from pure water 800g In solution.After so that it is fully dissolved, in the formalin 686g that 20~25 DEG C were added dropwise 36~38 mass % through 2 hours.So It is stirred 17 hours in 20~25 DEG C afterwards.Sulfuric acid 98g and water 552g is added thereto, is neutralized, the state is kept to place 2 days. The white solid generated in the solution after placement is washed with water 100mL.The white solid is dried in vacuo 48 in 50 DEG C Hour.
Then, the white solid obtained in the above described manner is dissolved in methanol 300mL, sulfuric acid 2g is added, is stirred at room temperature 24 Hour.Anionic ion exchange resin (Rohmand Haas corporations, Amberlyst IRA96SB) is added into the solution 15g stirs 1 hour, ion exchange resin is removed by filtration.Then, GBL500mL is added, is removed methanol with rotary evaporator It goes, GBL solution is made.It utilizes13C-NMR (Japan Electronics (strain) is made, GX-270) is analyzed it, and confirms to have obtained conduct Alkali soluble resins (be below denoted as (a1-1)) of the part through alkoxylated polyhydroxystyrene resin.By using GPC into Capable analysis, weight average molecular weight (Mw) are 8000 (conversions of GPC polystyrene), for through alkoxylated hydroxy styrenes Speech is the Drug delivery rate of 35mol% relative to every 1mol hydroxy styrenes.
The synthesis of 6 alkali soluble resins of synthesis example (a1-2)
Other than replacing (aO-1) of above-mentioned synthesis example 5 and using (a0-2), synthesized using same preparation method.For To as the alkali soluble resins (being denoted as below (a1-2)) through alkoxylated polyhydroxystyrene resin for, by using The analysis that GPC is carried out, weight average molecular weight (Mw) is 7500 (conversions of GPC polystyrene), relative to every 1mol hydroxy styrenes, alkane The Drug delivery rate of oxygroup is 55mol%.
The synthesis of 7 alkali soluble resins of synthesis example (a1-3)
Other than replacing (a0-1) of above-mentioned synthesis example 5 and using (a0-3), synthesized using same preparation method.For To as the alkali soluble resins (being denoted as below (a1-3)) through alkoxylated polyhydroxystyrene resin for, by using The analysis that GPC is carried out, weight average molecular weight (Mw) is 3500 (conversions of GPC polystyrene), relative to every 1mol hydroxy styrenes, alkane The Drug delivery rate of oxygroup is 69mol%.
The synthesis of synthesis example 8Novolac resins (e)
Under drying nitrogen stream, addition metacresol 70.2g (0.65mol), paracresol 37.8g (0.35mol), 37 mass % formaldehyde After aqueous solution 75.5g (formaldehyde 0.93mol), oxalic acid dihydrate 0.63g (0.005mol), methylisobutylketone 264g, in oil bath Middle dipping, makes reaction solution flow back on one side, carries out polycondensation reaction in 4 hours on one side.Then, the temperature for increasing oil bath through 3 hours, then Pressure in flask is reduced into 40~67hPa, volatile ingredient is removed, the resin of dissolving is cooled to room temperature, is obtained alkali-soluble The polymer solids of Novolac resins (e).The analysis carried out by using GPC, it is thus identified that weight average molecular weight (Mw) is 3,500. To gamma-butyrolacton (GBL) is added in obtained Novolac resins (e), it is 43 mass %'s to obtain solid component concentration Novolac resins (e) solution.
The synthesis of the closed loop polyimide resin (A) of synthesis example 9
Under drying nitrogen stream, PMDA-HH 4.48g (0.020mol), 6FDA 11.11g (0.025mol) are dissolved in NMP In 100g.3- amino-phenols 1.09g (0.010mol) is added together with NMP 20g thereto.In turn by BAHF 11.90g (0.033mol), DAE 1.00g (0.005mol), ED-6006.00g (0.010mol), SiDA 0.62g (0.003mol) with NMP 20g are added together, react in 60 DEG C 1 hour, are then stirred 4 hours in 180 DEG C.After stirring, solution is put into water In 2L, white precipitate is obtained.The precipitation is collected by filtering, after being washed with water 3 times, is carried out using 50 DEG C of vacuum driers Drying in 72 hours obtains the powder of closed loop polyimide resin (A).
The synthesis of the closed loop polyimide resin (B) of synthesis example 10
Under drying nitrogen stream, by PMDA-HH 1.12g (0.005mol), 6FDA 11.11g (0.025mol), ODPA 4.65g (0.015mol) is dissolved in NMP 100g.3- amino-phenols 1.09g (0.010mol) is added together with NMP 20g thereto. In turn by BAHF11.90g (0.033mol), DAE 1.00g (0.005mol), ED6006.00g (0.010mol), SiDA 0.62g (0.003mol) is added together with NMP 20g, reacts in 60 DEG C 1 hour, is then stirred 4 hours in 180 DEG C.Stirring knot Shu Hou obtains white precipitate by solution input water 2L.The precipitation is collected by filtering, after being washed with water 3 times, utilizes 50 DEG C vacuum drier carry out drying in 72 hours, obtain the powder of closed loop polyimide resin (B).
The synthesis of the closed loop polyimide resin (C) of synthesis example 11
Under drying nitrogen stream, CBDA 3.92g (0.020mol), 6FDA 11.11g (0.025mol) are dissolved in NMP 100g In.3- amino-phenols 1.09g (0.010mol) is added together with NMP 20g thereto.And then it is added together with NMP 20g BAHF 11.90g(0.033mol)、DAE 1.00g(0.005mol)、ED6006.00g(0.010mol)、SiDA 0.62g (0.003mol) is reacted 1 hour in 60 DEG C, is then stirred 4 hours in 180 DEG C.After stirring, by solution input water 2L Obtain white precipitate.The precipitation is collected by filtering, after being washed with water 3 times, it is small to carry out 72 using 50 DEG C of vacuum driers When dry, obtain the powder of closed loop polyimide resin (C).
The synthesis of the closed loop polyimide resin (D) of synthesis example 12
Under drying nitrogen stream, make CBDA 0.98g (0.005mol), 6FDA 11.11g (0.025mol), ODPA 4.65g (0.015mol) is dissolved in NMP 100g.BAHF 11.90g (0.033mol), DAE is added together with NMP 20g thereto 0.50g (0.003mol), ED6007.50g (0.013mol), SiDA 0.62g (0.003mol) are reacted 1 hour in 60 DEG C, are connect It and is stirred 4 hours in 180 DEG C, 5- norbornene -2,3- dicarboxylic acid anhydrides 1.64g is then added together with NMP 10g (0.010mol) is used as end-capping reagent, is reacted 1 hour in 60 DEG C.It is heavy by white is obtained in solution input water 2L after stirring It forms sediment.The precipitation is collected by filtering, after being washed with water 3 times, drying in 72 hours is carried out using 50 DEG C of vacuum driers, obtains The powder of closed loop polyimide resin (D).
The synthesis of the closed loop polyimide resin (E) of synthesis example 13
Under drying nitrogen stream, make CBDA 0.98g (0.005mol), 6FDA 11.11g (0.025mol), TDA-1004.50g (0.015mol) is dissolved in NMP 100g.BAHF 11.90g (0.033mol), DAE is added together with NMP 20g thereto 0.50g (0.003mol), ED6007.50g (0.013mol), SiDA 0.62g (0.003mol) are reacted 1 hour in 60 DEG C, are connect It and is stirred 4 hours in 180 DEG C, 5- norbornene -2,3- dicarboxylic acid anhydrides 1.64g is then added together with NMP 10g (0.010mol) is used as end-capping reagent, is reacted 1 hour in 60 DEG C.It is heavy by white is obtained in solution input water 2L after stirring It forms sediment.The precipitation is collected by filtering, after being washed with water 3 times, drying in 72 hours is carried out using 50 DEG C of vacuum driers, obtains The powder of closed loop polyimide resin (E).
The synthesis of the closed loop polyimide resin (F) of synthesis example 14
Under drying nitrogen stream, PMDA-HH 10.09g is made (O.045mol) to be dissolved in NMP 100g.Thereto with NMP 20g 3- amino-phenols 1.09g (0.010mol) is added together.And then be added together with NMP 20g BAHF 15.57g (0.043mol), DAE 1.00g (0.005mol), SiDA 0.62g (0.003mol) react 1 hour in 60 DEG C, then small in 180 DEG C of stirrings 4 When.After stirring, white precipitate will be obtained in solution input water 2L.The precipitation is collected by filtering, is washed with water 3 times Afterwards, drying in 72 hours is carried out using 50 DEG C of vacuum drier, obtains the powder of closed loop polyimide resin (F).
The synthesis of the closed loop polyimide resin (G) of synthesis example 15
Under drying nitrogen stream, CBDA 8.82g (0.045mol) is made to be dissolved in NMP 100g.Thereto together with NMP 20g 3- amino-phenols 1.09g (0.010mol) is added.And then BAHF 15.57g (0.043mol), DAE are added together with NMP 20g 1.00g (0.005mol), SiDA 0.62g (0.003mol) are reacted 1 hour in 60 DEG C, are then stirred 4 hours in 180 DEG C.It stirs After mixing, white precipitate will be obtained in solution input water 2L.The precipitation is collected by filtering, after being washed with water 3 times, profit Drying in 72 hours is carried out with 50 DEG C of vacuum driers, obtains the powder of closed loop polyimide resin (G).
The synthesis of the closed loop polyimide resin (H) of synthesis example 16
Under drying nitrogen stream, ODPA 13.96g (0.045mol) is made to be dissolved in NMP 100g.Thereto with NMP 20g mono- It rises and 3- amino-phenols 1.09g (0.010mol) is added.And then be added together with NMP 20g BAHF 11.90g (0.033mol), DAE 1.00g (0.005mol), ED6006.0g (0.010mol), SiDA 0.62g (0.003mol) react 1 hour in 60 DEG C, Then it is stirred 4 hours in 180 DEG C.After stirring, white precipitate will be obtained in solution input water 2L.It is collected by filtering The precipitation after being washed with water 3 times, carries out drying in 72 hours using 50 DEG C of vacuum driers, obtains closed loop polyimides tree The powder of fat (H).
The synthesis of the closed loop polyimide resin (I) of synthesis example 17
Under drying nitrogen stream, TDA-1006.01g (0.020mol), 6FDA 11.11g (0.025mol) is made to be dissolved in NMP In 100g.3- amino-phenols 1.09g (0.010mol) is added together with NMP 20g thereto.And then it is added together with NMP 20g BAHF 11.90g(O.033mol)、DAE 1.00g(O.005mol)、ED6006.Og(O.O10mol)、SiDA O.62g (O.003mol), it reacts in 60 DEG C 1 hour, is then stirred 4 hours in 180 DEG C.After stirring, by solution input water 2L Obtain white precipitate.The precipitation is collected by filtering, after being washed with water 3 times, it is small to carry out 72 using 50 DEG C of vacuum driers When dry, obtain the powder of closed loop polyimide resin (I).
The synthesis of the closed loop polyimide resin (J) of synthesis example 18
Under drying nitrogen stream, 6FDA 19.99g is made (O.045mol) to be dissolved in NMP 100g.Thereto with NMP 20g mono- It rises and 3- amino-phenols 1.09g (O.O10mol) is added.And then be added together with NMP 20g BAHF 11.90g (O.033mol), DAE 1.00g (O.005mol), ED6006.Og (O.010mol), SiDA 0.62g (0.003mol) react 1 hour in 60 DEG C, Then it is stirred 4 hours in 180 DEG C.After stirring, white precipitate will be obtained in solution input water 2L.It is collected by filtering The precipitation after being washed with water 3 times, carries out drying in 72 hours using 50 DEG C of vacuum driers, obtains closed loop polyimides tree The powder of fat (J).
The synthesis of 19 polybenzoxazole precursor (K) of synthesis example
Under drying nitrogen stream, BAHF 18.3g (0.05mol) is made to be dissolved in NMP 50g, glycidyl methyl ether 26.4g In (0.3mol), the temperature of solution is cooled to -15 DEG C.Being added dropwise in such a way that internal temperature is no more than 0 DEG C thereto makes hexichol Solution obtained from base ether dimethyl chloride 14.7g (Japanese pesticide (strain) system, 0.050mol) is dissolved in GBL 25g.Knot is added dropwise Shu Hou is persistently stirred 6 hours in -15 DEG C.After reaction, by the water 3L of methanol of the solution input comprising 10 mass %, make White precipitate is precipitated.The precipitation is collected by filtering, after being washed with water 3 times, it is small to carry out 72 using 50 DEG C of vacuum driers When dry, obtain alkali-soluble polybenzoxazole precursor (K).
The synthesis of 20 polyimide precursor resin of synthesis example (L)
Under drying nitrogen stream, make 4,4 '-diamino-phenyl ether (being denoted as DAE below) 7.51g (0.038mol), SiDA1.86g (0.007mol), 3- amino-phenols 1.09g (0.010mol) are dissolved in NMP 100g.It is added thereto with together with NMP 20g ODPA 13.96g (0.045mol) are reacted 1 hour in 20 DEG C, are then reacted 4 hours in 50 DEG C.Then, it was added dropwise and uses through 10 minutes Solution obtained from n,N-Dimethylformamide dimethylacetal 9.25g (0.08mol) is diluted by NMP 5g, it is anti-in 50 DEG C It answers 3 hours.After reaction, solution is put into water 2L, by filtering come the precipitation of collected polymer solid.And then use water 2L Then washing 2 times carries out drying in 20 hours using 80 DEG C of vacuum drier, obtains polyimide resin (K).
The synthesis of 21 polyimide resin of synthesis example (M)
Under drying nitrogen stream, DAE 8.11g (0.04mol), 3- amino-phenols 1.09g (0.010mol) is made to be dissolved in NMP In 100g.ODPA 13.96g (O.045mol) are added together with NMP 20g thereto, are reacted 1 hour in 20 DEG C, then in 50 DEG C reaction 4 hours.In turn, it is then stirred 5 hours in 180 DEG C.It is heavy by white is obtained in solution input water 2L after stirring It forms sediment.The precipitation is collected by filtering, after being washed with water 3 times, drying in 20 hours is carried out using 80 DEG C of vacuum driers, obtains Polyimide resin (M).
The synthesis of the closed loop polyimide resin (N) of synthesis example 22
Under drying nitrogen stream, CBDA 3.92g (O.020mol), 6FDA 11.11g is made (O.025mol) to be dissolved in NMP 100g In.3- amino-phenols 1.09g (O.010mol) is added together with NMP 20g thereto.And then BAHF is added together with NMP 20g 10.07g(O.028mol)、DAE 1.00g(O.005mol)、ED6001O.50g(O.O18mol)、SiDA O.62g (O.003mol), it reacts in 60 DEG C 1 hour, is then stirred 4 hours in 180 DEG C.After stirring, by solution input water 2L Obtain white precipitate.The precipitation is collected by filtering, after being washed with water 3 times, it is small to carry out 72 using 50 DEG C of vacuum driers When dry, obtain the powder of closed loop polyimide resin (N).
The synthesis of the closed loop polyimide resin (O) of synthesis example 23
Under drying nitrogen stream, CBDA 3.92g (0.020mol), 6FDA 11.11g (0.025mol) is made to be dissolved in NMP 100g In.3- amino-phenols 1.09g (O.010mol) is added together with NMP 20g thereto.And then BAHF is added together with NMP 20g 7.33g(0.020mol)、DAE 1.00g(0.005mol)、ED60015.00g(0.025mol)、SiDA 0.62g (0.003mol) is reacted 1 hour in 60 DEG C, is then stirred 4 hours in 180 DEG C.After stirring, by solution input water 2L Obtain white precipitate.The precipitation is collected by filtering, after being washed with water 3 times, it is small to carry out 72 using 50 DEG C of vacuum driers When dry, obtain the powder of closed loop polyimide resin (O).
The synthesis of synthesis example 24Novolac resins (f)
Metacresol 108.0g, methanol 108.0g, sodium hydroxide 40.0g are added into the three-necked bottle 1000ml replaced through nitrogen, on one side It is stirred, is warming up to 67 DEG C on one side, then carry out 30 minutes back flow reactions.Then, reaction solution is cooled to 40 DEG C, addition 92 Quality % paraformaldehyde 65.2g after being warming up to 67 DEG C again, carry out 5 hours back flow reactions.After reaction, liquid cooling will be reacted But to 30 DEG C hereinafter, 30 mass % sulfuric acid 140.0g were added dropwise through 30 minutes in such a way that reaction solution does not become 35 DEG C or more.It obtains Reaction solution pH be 4.9.And then ion exchange water 540.0g is added into reaction solution, stir 20 minutes and stands 20 minutes Afterwards, the water layer of separation is removed.After removing water layer, dioxane 108.0g is added, in 40 DEG C, with the pressure of 0.08MPa By residual moisture removing to less than 3 mass %.Methanol 432.0g, 96 mass % sulfuric acid 2.0g are added into reaction solution.It obtains The pH of reaction solution is 0.8.Reaction solution is warming up to 60 DEG C, 3 hours alkoxylations are carried out in 60 DEG C.After reaction, will Reaction solution is cooled to 30 DEG C hereinafter, 10 mass % hydrogen were added dropwise through 30 minutes in such a way that the temperature of reaction solution does not become 35 DEG C or more Aqueous solution of sodium oxide, until the pH of reaction solution is 9.0.The methylisobutylketone with separation solvent as washing is added into reaction solution (MIBK) 216.0g, ion exchange water 324.0g are stirred 20 minutes in 30 DEG C, and stand 20 minutes, and the water layer of separation is removed. And then ion exchange water 324.0g is added, repeat washing operation with ion exchange water, until removing the conductivity of water becomes 100 μ Scm or less.After washing, gamma-butyrolacton 300g is added, ion exchange water is carried out in 70 DEG C, with the pressure of 0.08MPa And MIBK evaporates, and obtains the Novolac resin solutions (f) that solid state component is 50 mass %.
By using the analysis that GPC is carried out, the weight average molecular weight (Mw) of obtained Novolac resin solutions (f) is 7000 (GPA Polystyrene converts), dispersion degree (Mw/Mn) is 7.5.It is based on13CNMR, alkoxyalkyl relative to every 1mol phenol skeleton rub Your number is 57mol%, and alkoxy rate is 100mol%.
Embodiment 1
The quinone two obtained in resin (A) 1O.5g obtained in alkali soluble resins (a1-1) 10.5g, synthesis example 9, synthesis example 1 is folded Nitrogen compound (a) 3.0g, crosslinking agent MX-2707.2g, KBM-4031.Og are added in GBL 25g, obtain normal Photosensitive resin The varnish A of composition.
Using comma coating machine, obtained varnish is coated on the PET film that thickness is 38 μm, drying in 8 minutes is carried out in 80 DEG C, Then the PP films that thickness is 10 μm are subjected to lamination and are used as protective film, obtain photosensitive film.It is adjusted, so that photosensitive film Film thickness is 10 μm.
Using obtained photosensitive film, carry out and plyability, the high drawing of silicon substrate be forthright, 5% weight reduction temperature is (heat-resisting Property) and pattern processability each evaluation.
Embodiment 2~33, comparative example 1~8
In addition to adding (A1) alkali soluble resins, (A2) alkali soluble resins, other additives, (B) photoacid generator and (C) crosslinking agent Dosage be changed to table 1, table 2-1 and table 2-2 it is such other than, utilize method similarly to Example 1 to make varnish.Using obtaining Photosensitive film, carry out and plyability, the high drawing of silicon substrate are forthright, 5% weight reduces temperature (heat resistance) and pattern is processed Each evaluation of property.
The molar ratio of the ingredient of (A2) alkali soluble resins is shown in table 1.
It will be evaluation result is shown in table 3-1 and table 3-2.
[table 3-1]
[table 3-2]
Reference sign
1 semiconductor element
2 passivating films
3 cured films
4 metal lines
5 cured films
6 substrates
7 cured films
8 cured films
9 metal films
10 metal lines
11 metal lines
12 electrodes
13 sealing resins
14 substrates
15 IDT electrodes
16 landing pads
17 hollow portions
18 corbels
19 coated materials
20 protection components
21 via conductors
22 solder projections
23 silicon wafers
24 A1 pads
25 passivating films
26 resins
27 cured films
28 metal films
29 metal lines
30 insulating films
31 barrier metals
32 solder projections

Claims (20)

1. photosensitive film contains:
(A1) alkali soluble resins of the structural unit indicated with general formula (1);
(A2) include in polyimides, polybenzoxazole, polyamidoimide, their precursor and their copolymer More than one alkali soluble resins;
(B) photoacid generator;And
(C) thermal cross-linking agent,
[chemical formula 1]
In general formula (1), R1Indicate that hydrogen atom or the alkyl of carbon atom number 1~5, a indicate that the integer in the range of 0~4, b indicate 1 Integer in the range of~3, R2For hydrogen atom, methyl, ethyl or propyl.
2. photosensitive film as described in claim 1, wherein the weight average molecular weight (Mw) of (A1) alkali soluble resins 3, In the range of 000~60,000.
3. photosensitive film as claimed in claim 1 or 2, wherein (A1) alkali soluble resins also has general formula (2) and general formula (3) at least either in the structural unit indicated,
[chemical formula 2]
In general formula (2), R3Indicate that hydrogen atom or the alkyl of carbon atom number 1~5, e indicate the integer in the range of 1~5,
[chemical formula 3]
In general formula (3), R4Indicate hydrogen atom or the alkyl of carbon atom number 1~5.
4. photosensitive film according to any one of claims 1 to 3, wherein the weight average molecular weight of (C) thermal cross-linking agent (Mw) it is 100~2,500.
5. photosensitive film as described in any one of claims 1 to 4, wherein (A2) alkali soluble resins, which has, is selected from carboxylic The substituent group of one or more of base, phenolic hydroxyl, sulfonic group or mercapto.
6. such as photosensitive film according to any one of claims 1 to 5, wherein (A2) alkali soluble resins has general formula (4) And at least either in the structural unit of (5) expression,
[chemical formula 4]
In general formula (4), R5Indicate two~quadrivalent organic radical group of carbon atom number 4~40;R6Indicate the two of carbon atom number 20~100 Valence organic group;n1Indicate the integer in the range of 10~100,000,
[chemical formula 5]
In general formula (5), R5Indicate two~quadrivalent organic radical group of carbon atom number 4~40;R6Indicate the two of carbon atom number 20~100 Valence organic group;R7Indicate hydrogen or the organic group of carbon atom number 1~20;n2Indicate the integer in the range of 10~100,000, p And q indicates the integer for meeting 0≤p+q≤2.
7. photosensitive film as claimed in claim 6, wherein the total amount for the repetitive unit that general formula (4) and (5) indicate is When 100mol%, R6For be with polyether structure and carbon atom number 20~100 organic group the general formula (4) and (5) Content is 10~80mol%.
8. photosensitive film as claimed in claim 7, wherein described with polyether structure and carbon atom number is 20~100 to have Machine group is the organic group that general formula (10) indicates,
[chemical formula 6]
In general formula (10), R54~R57Each independently represent the alkylidene of carbon atom number 1~6;R58~R65It each independently represents The alkyl of hydrogen, fluorine or carbon atom number 1~6;Wherein, the bracket of the structure and repetitive unit y that are indicated in the bracket of repetitive unit x The structure of interior expression is different;In addition, the structure indicated in the bracket of repetitive unit z and the knot indicated in the bracket of repetitive unit y Structure is respectively different;X, y, z each independently represents 0~35 integer.
9. the photosensitive film as described in any one of claim 6~8, wherein the repetitive unit that general formula (4) and (5) indicate When total amount is 100mol%, R5For be with alicyclic structure and carbon atom number 4~40 organic group the general formula (4) and (5) content is 10~80mol%.
10. such as photosensitive film according to any one of claims 1 to 9, the photosensitive film also contains (H) general formula (13) and indicates Compound,
[chemical formula 7]
In general formula (13), R71~R73Indicate any one of O atom or S atom, N atoms, and R71~R73At least one of table Show S atom;L indicates 0 or 1, when l is 0, R71Indicate oxygen atom or sulphur atom, when l is 1, R71Indicate nitrogen-atoms;M, n indicate 1 or 2;R74~R76Each independently represent hydrogen atom or the organic group of carbon atom number 1~20.
11. such as photosensitive film according to any one of claims 1 to 10, (C) thermal cross-linking agent also includes to have general formula (12) thermal cross-linking agent of the structural unit indicated,
[chemical formula 8]
In general formula (12), R69And R70Each independently represent hydrogen atom or methyl;R68For the alkylene with 2 or more carbon atom number The bivalent organic group of base, and be straight-chain, branched and ring-type.
12. the photosensitive film as described in any one of claim 1~11, it is 3~45 μm that the photosensitive film, which has film thickness, Photosensitive layer.
13. photosensitive film as claimed in claim 12, wherein there is protective film on the photosensitive layer, in the photosensitive layer There is down support membrane.
14. cured film, being will be obtained from the photosensitive film solidification described in any one of claim 1~13.
15. interlayer dielectric or semiconductor protection film, configured with the cured film described in claim 14.
16. electronic unit or semiconductor devices, the embossed pattern layer with the cured film described in claim 14.
17. electronic unit or semiconductor devices, wherein have described in claim 14 with 2~40 μm of film thickness on substrate Cured film, and the wiring with copper in cured film also with 2~40 μm of film thickness there is the cured film described in claim 14 to make Insulating film between thin copper film.
18. electronic unit or semiconductor devices, wherein the relief figure of the cured film with photosensitive polymer combination on substrate Pattern layer is as Zhi Chengcai, with the cured film described in claim 14 as coated material also on the Zhi Chengcai, in the branch The opening portion of the embossed pattern layer of corbel is configured with the coated material, and in being surrounded by Zhi Chengcai, coated material and substrate Empty portion.
19. electronic unit or semiconductor devices, wherein (S-1) upper layer part for being 2~40 μm with (T-1) layer difference on substrate (S-2) lower layer part,
It is gone up configured with the cured film described in claim 14 in (S-1) upper layer part and the respective of (S-2) lower layer part,
The cured film described in claim 14 that is configured in described (S-1) upper layer part, be configured in described (S-2) lower layer part Claim 14 described in cured film (T-2) layer difference be 5 μm or less.
20. the manufacturing method of electronic unit or semiconductor devices, to be made using the photosensitive film described in claim 1~13 The method of manufacturing semiconductor device, the manufacturing method include following processes:
Photosensitive film heating is crimped on substrate by the temperature in 40~150 DEG C, to form photonasty envelope Process;
The process that the photonasty envelope is exposed across exposed mask;
The process that the exposure portion of the photonasty envelope is removed using alkaline-based developer and is developed.
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