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CN107922708A - Resin combination, photosensitive polymer combination, resin film and electronic device - Google Patents

Resin combination, photosensitive polymer combination, resin film and electronic device Download PDF

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Publication number
CN107922708A
CN107922708A CN201680048062.7A CN201680048062A CN107922708A CN 107922708 A CN107922708 A CN 107922708A CN 201680048062 A CN201680048062 A CN 201680048062A CN 107922708 A CN107922708 A CN 107922708A
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Prior art keywords
formula
resin
polymer
combination
organic group
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Chinese (zh)
Inventor
穴田亘平
大西治
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Publication of CN107922708A publication Critical patent/CN107922708A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions 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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

The resin combination of the present invention includes phenolic resin and containing with the polymer of the repetitive unit shown in following formula (1).In formula (1), RX、RYIt is separately hydrogen or the organic group of carbon number 1~3.

Description

Resin combination, photosensitive polymer combination, resin film and electronic device
Technical field
The present invention relates to resin combination, photosensitive polymer combination, resin film and electronic device.
Background technology
Phenolic resin is due to excellent in resolution and has high-fire resistance and mechanical strength, studies various in composition Application in the resin film of electronic device.
For example, Patent Document 1 discloses the superstructure technologies used in the manufacture that can act as the elements such as IC, LSI With the positive light anti-etching agent of resist.More specifically, disclose comprising by metacresol novolac resin and adjacent first The resin compound and the composition of 1,2- quinone di-azido compounds that phenol novolac resin is formed.
Also, according to the document, by using such composition, using the teaching of the invention it is possible to provide a kind of sensitivity, film residual rate and with branch The positive light anti-etching agent of the excellent adhesion of support body.
Also, in recent years it has been proposed that containing making to have the phenolic compounds of specific structure and aliphatic aldehyde compound condensation and Obtained novolak phenolics as required component positive light anti-etching agent composition (for example, referenced patent document 2)。
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2-55359 publications
Patent document 2：Japanese Unexamined Patent Publication 2013-174702 publications
The content of the invention
The invention technical task to be solved
However, needing the level of higher as the required heat resistance of resin film for forming electronic device, presently, there are Resin combination comprising phenolic resin can not meet the demand.
Also, also there is the research and development hysteresis for the photosensitive polymer combination comprising phenolic resin there are this background Actual conditions.
In light of this situation, the present invention provides a kind of excellent heat resistance, such as energy when photosensitive polymer combination is made Enough balances show the resin combination of excellent sensitivity and high-fire resistance well.
For solving the means of technical task
According to the present invention, there is provided a kind of resin combination, it includes phenolic resin and contains the repetition shown in following formula (1) The polymer of unit.
(in formula (1), RX、RYIt is separately hydrogen or the organic group of carbon number 1~3.)
Also, according to the present invention, there is provided one kind includes the acid anhydrides of the polymer containing the repetitive unit shown in following formula (1) Position forms the resin combination of the ester compounds of ester bond with the phenolic hydroxyl group that phenolic resin possesses.
(in formula (1), RX、RYSeparately represent the organic group of hydrogen or carbon number 1~3.)
Also, according to the present invention, there is provided a kind of photosensitive polymer combination comprising above-mentioned resin combination and emulsion.
Also, according to the present invention, there is provided a kind of resin film for including above-mentioned resin combination.
Also, according to the present invention, there is provided a kind of resin film for including above-mentioned photosensitive polymer combination.
Also, according to the present invention, there is provided a kind of electronic device for possessing above-mentioned resin film.
Invention effect
In accordance with the invention it is possible to a kind of excellent heat resistance is provided, can for example be put down when photosensitive polymer combination is made Weighing apparatus property shows the resin combination of excellent sensitivity and heat resistance well, and has used the resin film of the resin combination And electronic device.
Brief description of the drawings
Above-mentioned purpose and other objects, features and advantages by preferred embodiment set forth below and its it is subsidiary with Lower attached drawing is further clear and definite.
Fig. 1 is the profile of an example for the electronic device for representing present embodiment.
The infrared absorpting light spectra of composition obtained from Fig. 2 is polymer 2 used in embodiment and makes its modification.
Embodiment
Hereinafter, suitably embodiment is illustrated using attached drawing.Wherein, in all of the figs, will to same composition Part marks identical symbol, suitably omits the description.Also, unless otherwise noted, "~" is represented with up to following.
[resin combination]
First, the resin combination of present embodiment is illustrated.
The resin combination of present embodiment is as follows.
A kind of resin combination, it includes phenolic resin and containing with the polymer of the repetitive unit shown in following formula (1).
(in formula (1), RX、RYIt is separately hydrogen or the organic group of carbon number 1~3.)
The resin combination of present embodiment is compared with the resin combination comprising phenolic resin that presently, there are, Neng Goubiao Reveal the heat resistance of higher.
It is although the detailed mechanism is not yet clear, such as it is considered that as follows：Although comprising phenolic resin and containing above-mentioned The polymer of repetitive unit shown in formula (1), but construction unit phase of the phenolic hydroxyl group that possesses of phenolic resin shown in formula (1) Effect, as a result, polymer forms close connecting structure with phenolic resin.
The resin combination of this present embodiment is suitable for photosensitive polymer combination.The photosensitive polymer combination Resin combination and emulsion can be included.
Hereinafter, each component of the resin combination to forming present embodiment illustrates.
(phenolic resin)
First, the phenolic resin included to the resin combination of present embodiment illustrates.
The phenolic resin of present embodiment can use conventionally known phenolic resin.As above-mentioned phenolic resin, have no It is particularly limited to, such as novolak phenolics, resol type phenol resin, aryl alkene fundamental mode phenolic resin etc. can be enumerated. As phenolic resin, a kind in them is can be used alone, two or more with different weight average molecular weight can also be used in combination, The one kind or two or more prepolymer with them can also be used in combination.Wherein, preferably using novolak phenolics.
As long as novolak phenolics make phenols and aldehydes in the presence of no catalyst or acidic catalyst into The resin that row is reacted and obtained, can suitably select according to purposes.For example, random phenolic varnish type or height can also be used The phenolic resin of ortho position phenolic varnish type.
Wherein, which usually passes through the molar ratio (aldehydes/phenols) in aldehydes relative to phenols Control is reacted and obtained on the basis of 0.5~1.0.
As the concrete example of used phenols when preparing the novolak phenolics, such as phenol, neighbour can be enumerated Cresols, metacresol, paracresol, xylenols, induced by alkyl hydroxybenzene, catechol, resorcinol etc..Also, those phenols can be independent It is used in mixed way using or by two or more.
In addition, as used aldehydes when preparing novolak phenolics, such as can use：Formaldehyde, poly The aldehyde compounds such as formaldehyde, benzaldehyde；Material as the generating source of these aldehyde compounds；Or solution of these aldehyde compounds etc.. Wherein, these aldehydes can be used alone or be used in mixed way two or more.
It is preferably more than 300 as the molecular weight of the phenolic resin of present embodiment, such as in terms of weight average molecular weight (Mw), More preferably more than 1000, more preferably more than 2000, particularly preferably more than 3000.It is by weight average molecular weight (Mw) More than above-mentioned lower limit, the mechanical strength and heat resistance that can make resin combination and the resin film obtained by resin combination carry It is high.
It is preferably less than 20000 as the molecular weight of the phenolic resin, such as in terms of weight average molecular weight (Mw), more preferably Less than 18000, more preferably less than 15000.It is below above-mentioned upper limit value by weight average molecular weight (Mw), can realizes system Operational raising during molding resins composition, the raising of mouldability when obtaining by resin combination resin film.
Further, it is possible to realize the raising and not of the sensitivity of resin combination and the resin film obtained by resin combination The amount of precipitation of solvent components is reduced.
Also, the weight average molecular weight can be based on making with following polymer likewise by gel permeation chromatograph (GPC) Calculated with the calibration curve that polystyrene standards matter is made.
(polymer)
The polymer of present embodiment contains the repetitive unit shown in above-mentioned formula (1).That is, the polymer of present embodiment is The polymer of unit containing the unsaturated carboxylic acid anhydrides from intramolecular with cyclic structure, is, for example, unsaturated carboxylic acid anhydrides and its The copolymer of his monomer.In the present embodiment, intramolecular have cyclic structure unsaturated carboxylic acid anhydrides may be selected from maleic anhydride, Citraconic anhydride, dimethyl maleic anhydride or their derivative, are also selected from maleic anhydride, citraconic anhydride, dimethyl Malaysia Acid anhydrides.They may be used alone, or two or more kinds may be used in combination.
As the unsaturated carboxylic acid anhydrides from intramolecular possessed by the polymer of present embodiment with cyclic structure Unit, such as the unit for being derived from intramolecular and there are the unsaturated carboxylic acid anhydrides of cyclic structure shown in following formula (1) can be used, also The unit from maleic anhydride shown in following formula (6) can be used.
(in formula (1), RX、RYIt is separately hydrogen or the organic group of carbon number 1~3)
In the present embodiment, in above-mentioned formula (1), RXAnd RYSuch as preferably it is separately hydrogen or carbon number 1~3 Organic group, be separately more preferably the organic group of hydrogen or carbon number 1, further preferred RXFor hydrogen and RYFor hydrogen Or the organic group of carbon number 1, still more preferably RXAnd RYFor hydrogen.
In the present embodiment, in above-mentioned formula (1), as composition RXAnd RYOrganic group, such as alkyl, alkene can be enumerated Base, alkynyl, alkylidene, cycloalkyl and heterocyclic radical.
As alkyl, such as methyl, ethyl, n-propyl can be enumerated.As alkenyl, such as pi-allyl and ethene can be enumerated Base.As alkynyl, acetenyl can be enumerated.As alkylidene, such as methine and ethylidine can be enumerated.As cycloalkyl, such as Cyclopropyl can be enumerated.As heterocyclic radical, such as epoxy group and oxetanylmethoxy can be enumerated.
The other monomers for having the unsaturated carboxylic acid anhydrides copolymerization of cyclic structure with the intramolecular can be according to using resin group The purposes of compound and suitably select.
As more specifically example, can enumerate：Norbornene, norbornadiene, two rings [2.2.1]-hept-2-ene" are (usual Name：2- norbornene), 5- methyl -2- norbornene, 5- ethyl -2- norbornene, 5- butyl -2- norbornene, 5- hexyls - 2- norbornene, 5- decyl -2- norbornene, 5- pi-allyl -2- norbornene, 5- (2- acrylic) -2- norbornene, 5- (1- methyl -4- pentenyls) -2- norbornene, 5- acetenyl -2- norbornene, 5- benzyl -2- norbornene, 5- phenethyls - The Norbornene derivatives such as 2- norbornene；The indene monomers such as indenes, 2- methyl indenes, 3- methyl indenes；1,5,9- cyclodoecatrienes, Cis- trans- 1,5,9- cyclodoecatrienes, trans- trans- 1,5,9- cyclodoecatrienes, trans- cis- 1,5,9- rings 12 The alicyclic ring class monomers such as carbon triolefin, cis- cis- 1,5,9- cyclodoecatrienes；Styrene, vinyltoluene, α-methylstyrene Deng styrene monomer；The vinyl monomers such as vinyl chloride, vinylidene chloride；The fluorine-containing second such as perfluoroethylene, perfluoropropene, vinylidene Vinyl monomer；The siliceous vinyl monomer such as vinyltrimethoxysilane, vinyltriethoxysilane；Acrylonitrile, methyl-prop The vinyl monomer of the nitrile group-containings such as alkene nitrile；The vinyl monomer of the amide-containings such as acrylamide, Methacrylamide；Vinyl acetate The vinyl esters such as ester, vinyl propionate, new vinyl acetate acid, vinyl benzoate, cassia bark vinyl acetate；The alkene such as ethene, propylene Hydro carbons；Butadiene, isoprene equiconjugate dienes；The allylic monomers such as allyl chloride, allyl alcohol；Maleimide, N- Methylmaleimido, n-ethylmaleimide, N- propylmaleimides, N- isopropylmaleimides, N- butyl horses Carry out the N- alkyl maleimides such as acid imide, N- isobutyl groups maleimide, N- tert-butylmaleimides；N- cyclohexyl Malaysia Acid imide, N- cyclopentylmaleimides, N- norbornies maleimide, N- cyclohexyl methyls maleimide, N- rings penta The N- cycloalkylmaleimides such as ylmethyl maleimide；N-phenylmaleimide, N- chlorophenylmaleimides, N- first Base phenyl maleimide, N- naphthyls maleimide, N- hydroxyphenyl-maleimides, N- methoxyphenyl maleimides The N- aryl maleimides such as amine, N- carboxyl phenyls maleimide, N- nitrobenzophenone maleimides；Except N- alkyl Malaysia acyl Beyond imines, N- cycloalkylmaleimides, N- aryl maleimides, the Malaysia of N- hydroxy maleimides etc. can be also enumerated Acid imide monomer etc..They can be used alone a kind, can also be used in combination two or more different.
As above-mentioned other monomers, preferably using the norbornene-type monomers in alicyclic ring class monomer, styrene monomer, indenes Class monomer, maleimide monomer.That is, the polymer of present embodiment preferably also contains and is dropped selected from being derived from shown in formula (2) The unit from styrene monomer shown in the unit of norbornene type monomer, formula (3), be derived from indene monomer shown in formula (7) Unit and formula (8) shown at least one of the unit from maleimide monomer unit.They can individually contain 1 Kind, different units of more than two kinds can also be contained.
These units are contained by polymer, the resin combination of present embodiment can be made and obtained by resin combination Resin film heat resistance improve.
(in formula (2), R1、R2、R3And R4It is separately hydrogen or the organic group of carbon number 1~30；N for 0,1 or 2。)
(in formula (3), Ra is separately the organic group of carbon number 1~30；M is less than more than 05 integer.)
(in formula (7), R5To R11It is separately hydrogen or the organic group of carbon number 1~3.)
(in formula (8), R12It independently is the organic group of hydrogen or carbon number 1~10.)
In the present embodiment, in above-mentioned formula (2), R1~R4Such as separately having for hydrogen or carbon number 1~30 Machine group, is preferably separately hydrogen or the organic group of carbon number 1~10, more preferably separately former for hydrogen or carbon The organic group of subnumber 1~3, is separately further preferably hydrogen or the organic group of carbon number 1.Also, above-mentioned formula (2) in, n is, for example, 0,1 or 2, is preferably 0 or 1, and more preferably 0.
In the present embodiment, in above-mentioned formula (3), Ra is separately for example the organic of hydrogen or carbon number 1~30 Group, is preferably separately hydrogen or the organic group of carbon number 1~10, is more preferably separately hydrogen or carbon atom The organic group of number 1~3, is separately further preferably hydrogen or the organic group of carbon number 1.Also, above-mentioned formula (3) In, m is, for example, less than more than 05 integer, is preferably the integer of less than more than 03 integer, more preferably less than more than 01.
In the present embodiment, in above-mentioned formula (7), R5~R11Such as separately having for hydrogen or carbon number 1~3 Machine group, is preferably separately hydrogen or the organic group of carbon number 1, is further preferably separately hydrogen.
In the present embodiment, in above-mentioned formula (8), R12Such as the organic group of hydrogen or carbon number 1~10 independently is, It is preferably independently hydrogen or the organic group of carbon number 1~5, independently more preferably is the organic group of hydrogen or carbon number 1~3 Group, independently further preferably is the organic group of hydrogen or carbon number 1.
Form R1~R4, Ra carbon number 1~30 organic group can contain in its structure selected from O, N, S, P and More than a kind of atom in Si.Also, form R5~R11The organic group of carbon number 1~3 can contain in its structure More than a kind of the atom in O, N, S, P and Si.Also, form R12The organic group of carbon number 1~10 can be at it Contain more than a kind of the atom in O, N, S, P and Si in structure.Also, form R1~R4、Ra、R5~R11And R12Have Machine group all can be not have the group of acidic functionality.Thereby, it is possible to easily control the acid number of polymer.
In the present embodiment, as composition R1~R4, Ra organic group, such as alkyl, alkenyl, alkynyl, secondary can be enumerated Alkyl, aryl, aralkyl, alkaryl, cycloalkyl and heterocyclic radical.
As alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth can be enumerated Base, amyl group, neopentyl, hexyl, heptyl, octyl group, nonyl and decyl.As alkenyl, such as pi-allyl, pentenyl and second can be enumerated Alkenyl.As alkynyl, acetenyl can be enumerated.As alkylidene, such as methine and ethylidine can be enumerated.As aryl, such as Tolyl, xylyl, phenyl, naphthyl and anthryl can be enumerated.As aralkyl, such as benzyl and phenethyl can be enumerated.As Cycloalkyl, such as adamantyl, cyclopenta, cyclohexyl and cyclooctyl can be enumerated.As heterocyclic radical, for example, can enumerate epoxy group and Oxetanylmethoxy.
In the present embodiment, as composition R5~R11Organic group, such as alkyl, alkenyl, alkynyl, secondary alkane can be enumerated Base, cycloalkyl and heterocyclic radical.
As alkyl, such as methyl, ethyl, n-propyl can be enumerated.As alkenyl, such as pi-allyl and ethene can be enumerated Base.As alkynyl, acetenyl can be enumerated.As alkylidene, such as methine and ethylidene can be enumerated.As cycloalkyl, such as Cyclopropyl can be enumerated.As heterocyclic radical, such as epoxy group and oxetanylmethoxy can be enumerated.
In the present embodiment, as composition R12Organic group, such as hydrogen or above-mentioned R can be used1~R4, Ra institutes The organic group of carbon number 1~10 in the organic group of illustration.
In addition, form R1~R4、Ra、R5~R11And R12Alkyl, alkenyl, alkynyl, alkylidene, aryl, aralkyl, alkane virtue The hydrogen atom of more than 1 of base, cycloalkyl and heterocyclic radical can be substituted by halogen atom.As halogen atom, can enumerate fluorine, chlorine, bromine and Iodine.Wherein, the hydrogen atom of more than 1 of optimizing alkyl is substituted by the haloalkyl of halogen atom.By making R1~R4、Ra、R5~ R11、R12In at least any one be haloalkyl, can reduce the dielectric of the cured film when forming cured film using polymer Constant.Also, by forming haloalkyl alcohol radical, the dissolubility for alkaline-based developer can not only be moderately adjusted, and Resistance to thermochromism can be improved.
In addition, from the viewpoint of the translucency for improving the film formed comprising polymer, preferably R1~R4、Ra、R5~R11 And R12In any one be hydrogen, such as using formula (2) construction unit in the case of, preferably R1~R4It is hydrogen.Such as In the case of construction unit using formula (3), preferably Ra is hydrogen.Such as in the case of using the construction unit of formula (7), preferably R5~R11For hydrogen.Such as in the case of using the construction unit of formula (8), preferably R12For hydrogen.
In order to adjust the molecular weight of polymer, chain-transferring agent can be suitably used.As chain-transferring agent, such as can enumerate： 3- mercaptopropionic acid octadecanes ester, pentaerythrite four (3-thiopropionate), β-mercaptopropionic acid, 3- mercaptopropionic acids methoxybutyl, 3- mercaptopropionic acid octadecanes ester, trimethylolpropane tris (3-thiopropionate), three-[(3- mercaptopropionyls epoxide)-ethyl] are different The β-mercaptopropionic acid class such as cyanurate；The naphthoquinones classes such as 2 hydroxy 1,4 naphthoquinone (lawsone), 1,4- naphthoquinones；N-hexyl mercaptan, n-octyl sulphur The thio-alcohols such as alcohol, n-dodecyl mercaptan, tert-dodecylmercaotan, thioacetic acid, mercaptopropionic acid；Dimethyl disulfide xanthic acid The xanthan acids such as ester, dithiodiisopropyl xanthate；And triethoxysilane, terpinolene, α-methylstyrene two Polymers etc..
Polymer before being reacted with the phenolic resin in present embodiment is utilizing such as GPC (gel infiltration colors Spectrometry, Gel Permeation Chromatography) obtained from molecular weight distribution curve, molecular weight is below 1000 Peak area can be overall less than 3%, can also be less than 2%.
In this way, the ratio of the peak area by the molecular weight of molecular weight distribution curve that will be obtained using GPC below 1000 Above range is set to, the pattern form of film that is made of the resin combination comprising polymer can be made good.Therefore, it is possible to carry Height possesses Reliability of Microprocessor of the film as electronic devices such as the liquid crystal display device of permanent film, solid-state imagers.
In addition, the lower limit of the amount of low molecular weight compositions in polymer is not particularly limited.However, in present embodiment Polymer allows the peak area in the molecular weight distribution curve middle-molecular-weihydroxyethyl obtained by GPC below 1000 to be overall 0.01% Situation above.
Polymer such as Mw (weight average molecular weight)/Mn (numbers before being reacted with the phenolic resin in present embodiment Average molecular weight) it is less than more than 1.5 2.5.Wherein, Mw/Mn is the dispersion degree for the width for representing molecular weight distribution.
It was found by the inventors of the present invention that by controlling the molecular weight distribution of polymer in certain scope, for by The film that the polymer is formed, the deformation of pattern when can suppress to cure.Therefore, by the way that the Mw/Mn of polymer is set to above-mentioned model Enclose, the shape of film that is made of the resin combination comprising polymer can be made good.In addition, this effect as above institute at the same time Show especially pronounced in the case of reduce polymer low molecular weight compositions with stating.
Also, the molecular weight Mw (weight average molecular weight) of polymer is, for example, 1, more than 500 30, less than 000.
Wherein, weight average molecular weight (Mw), number-average molecular weight (Mn) and molecular weight distribution (MW/Mn) for example using according to by The polystyrene scaled value that the calibration curve for the polystyrene standard (PS) that GPC is measured is obtained.Determination condition is for example as follows It is shown.
The gel permeation chromatograph device HLC-8320GPC of TOSOH CORPORATION productions
Column：The TSK-GEL Supermultipore HZ-M of TOSOH CORPORATION productions
Detector：Phase chromatography-use RI detectors
Measuring temperature：40℃
Solvent：THF
Sample solution concentration：2.0mg/ milliliter
In addition, low molecular weight compositions amount in polymer is for example based on the relevant data of molecular weight measured by GPC, Calculated according to the area summation of the component equivalent to molecular weight below 1000 ratio shared in molecular weight distribution entire area Go out.
(manufacture method of polymer)
The polymer of present embodiment can be by making intramolecular have the unsaturated carboxylic acid anhydrides and other lists of cyclic structure Body is copolymerized and is obtained.The manufacture method can use conventionally known method.Hereinafter, enumerate comprising above-mentioned formula (2) Suo Shi Repetitive unit polymer manufacture method exemplified by, it is described below.
(polymerization procedure (processing S1))
First, prepare using the norbornene-type monomers shown in following formula (2a) and the maleic anhydride as monomer.At formula (2a) In shown norbornene-type monomers, n, R1~R4Can be identical with above-mentioned formula (2).
As the norbornene-type monomers shown in formula (2a), specific enumerable two ring [2.2.1]-hept-2-ene" (trivial name： 2- norbornene).The norbornene-type monomers with alkyl are further used as, 5- methyl -2- norbornene, 5- second can be enumerated Base -2- norbornene, 5- butyl -2- norbornene, 5- hexyl -2- norbornene, 5- decyl -2- norbornene etc.；As tool There are the norbornene-type monomers of alkenyl, 5- pi-allyl -2- norbornene, 5- (2- acrylic) -2- norbornene, 5- can be enumerated (1- methyl -4- pentenyls) -2- norbornene etc.；As the norbornene-type monomers with alkynyl, 5- acetenyls -2- can be enumerated Norbornene etc.；As the norbornene-type monomers with aralkyl, 5- benzyl -2- norbornene, 5- phenethyls -2- can be enumerated Norbornene etc..
In addition, as norbornene-type monomers, the R in formula (2a) can be used1、R2、R3、R4Included in the structure of group The norbornene-type monomers of the functional group such as the group with bridging property or the group containing halogen atoms such as fluorine.
As norbornene-type monomers, can use more than either of which kind.Wherein, from the heat resistance of polymer with From the viewpoint of the balance of translucency, preferably using two rings [2.2.1]-hept-2-ene" (trivial name：2- norbornene).
Then, the norbornene-type monomers shown in formula (2a) carry out addition polymerization with maleic anhydride.Here, pass through radical polymerization Close, form the copolymer (copolymer 1) of the norbornene-type monomers and maleic anhydride shown in formula (2a).
Molar ratio (mole of the compound shown in formula (2a) of norbornene-type monomers and maleic anhydride shown in formula (2a) Number:The molal quantity of maleic anhydride) it is preferably 0.5:1~1:0.5.Wherein, from the viewpoint of control molecular structure, preferred formula The molal quantity of norbornene-type monomers shown in (2a):Molal quantity=0.8 of maleic anhydride:1~1:0.8.
In addition, in the addition polymerization, in addition to above-mentioned norbornene-type monomers and maleic anhydride, can also add to carry out The monomer of copolymerization.As this monomer, the compound that intramolecular includes the group with olefinic double bond can be enumerated.Here, conduct The concrete example of group with olefinic double bond, can enumerate pi-allyl, acryloyl group, methylacryloyl, dimaleoyl imino or Aromatic ethenyl such as styryl or indenyl etc..
Furthermore it is also possible to replace above-mentioned maleic acid using unsaturated carboxylic acid anhydrides of other intramoleculars with cyclic structure Acid anhydride.
It is polymerize as polymerization, such as preferably using radical polymerization initiator and chain-transferring agent as needed Method.In this case, the methods of suspension polymerisation, polymerisation in solution, dispersin polymerization, emulsion polymerization can be used.Wherein, preferably Polymerisation in solution.In polymerisation in solution, each monomer can disposably be added to whole amount to carry out, can also be by a part added to instead Container is answered, then remaining monomer is added dropwise to carry out.
For example, by the way that norbornene-type monomers, maleic anhydride and the polymerization initiator shown in formula (2a) are dissolved in solvent In, heat afterwards the stipulated time, thus the norbornene-type monomers shown in formula (2a) carry out polymerisation in solution with maleic anhydride.Add Hot temperature is, for example, 50~80 DEG C, when heating time is 10~20 small.
As solvent used in polymerization, such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, acetic acid can be used It is more than any of ethyl ester etc..
As radical polymerization initiator, can use more than any of azo-compound and organic peroxide.
As azo-compound, such as double (2 Methylpropionic acids) two of azobis isobutyronitrile (AIBN), 2,2'- azos can be enumerated Methyl esters, 1,1'- azos are double (cyclohexane carbonitrile) (ABCN), can use more than either of which kind.
In addition, as organic peroxide, such as hydrogen peroxide, di-t-butyl peroxide (DTBP), peroxidating can be enumerated Benzoyl (benzoyl peroxide, BPO) and methyl ethyl ketone peroxide (MEKP), can use either of which kind with On.
The amount (molal quantity) of radical polymerization initiator is preferably norbornene-type monomers and maleic acid shown in formula (2a) The 1%~10% of total molal quantity of acid anhydride.By the way that the amount of polymerization initiator is suitably set within the above range, and suitably set Determine reaction temperature, reaction time, the amount of chain-transferring agent, the weight average molecular weight (Mw) of the polymer obtained can be adjusted suitable When scope.
By the polymerization process (processing S1), will can have shown in repetitive unit and the formula (2) shown in above-mentioned formula (1) The copolymer 1 polymerization of repetitive unit.
Wherein, in copolymer 1, the R of the structure of formula (2)1It is preferred that be common in each repetitive unit, but can also be It is different in each repetitive unit.In R2~R4In similarly.
Copolymer 1 can be that the repetitive unit shown in formula (1) is randomly configured with the repetitive unit shown in formula (2) Structure, can also be the structure alternately configured.Also, it can also be the norbornene-type monomers shown in formula (2a) and horse Carry out acid anhydrides and carry out the structure that block copolymerization forms.Wherein, from the resin group ensured using the polymer manufactured by present embodiment From the viewpoint of the deliquescent uniformity of compound, the repetitive unit shown in preferred formula (1) is handed over the repetitive unit shown in formula (2) The structure alternately configured.That is, copolymer 1 is for example in the case of norbornene-type monomers and maleic anhydride, preferably For with the structure of the repetitive unit shown in following formula (4).
(in formula (4), n, R1~R4It is identical with above-mentioned formula (2).That is, n is any one in 0,1,2.R1~R4For hydrogen or carbon The organic group of atomicity 1~30.R1~R4It can be the same or different.Also, the integer that a is less than more than 10 200.)
Here, the R of the structure of formula (4)1It is preferred that be common in each repetitive unit, but can also be in each repetitive unit In it is different.In R2~R4In it is also identical.
(low molecular weight compositions removing step (processing S2))
Then, as needed in the organic layer comprising the low molecular weight compositions such as copolymer 1 and residual monomer and oligomer, A large amount of poor solvents, such as hexane or methanol are added, makes the polymer solidification precipitation comprising copolymer 1.Here, as low molecule Component is measured, includes residual monomer, oligomer and polymerization initiator etc..Then, filtered, do obtained coagulum It is dry.Thus, polymer after removing low molecular weight compositions, using copolymer 1 as main component (mainly generating thing) can be obtained.
In the resin combination of present embodiment, the content of polymer is excellent relative to above-mentioned 100 mass parts of phenolic resin Elect as more than 5 mass parts, more preferably more than 10 mass parts, more preferably more than 15 mass parts, particularly preferably 20 matter Measure more than part.
Also, in the resin combination of present embodiment, the content of polymer is relative to above-mentioned 100 mass of phenolic resin Part is preferably 100 below mass part, and more preferably 70 is below mass part, and more preferably 50 is below mass part, particularly preferably It is below mass part for 35.
By being set as such scope, the appropriate interaction with above-mentioned phenolic resin can be brought, is more conducive to Improve heat resistance.
Even if for example, above-mentioned polymer include above-mentioned formula (7) shown in repetitive unit in the case of, can also be by making With the indene monomer shown in following formula (7a), the same method of the monomer and polymer phase with the repetitive unit comprising formula (2) is utilized Manufactured.
(in formula (7a), R5~R11It is identical with formula (7).)
The resin combination of present embodiment includes above-mentioned phenolic resin and polymer, preferably comprises the formula in polymer (6) what the construction unit (i.e. maleic anhydride units) shown in was bonded with the phenolic hydroxyl group that phenolic resin possesses via ester bond Compound (ester compounds).
It is considered that in the resin combination of present embodiment, pass through the phenolic hydroxyl group and maleic anhydride addition, there is provided With the half ester shown in following formula (5).Due to the ester bond in the formula (5), resin combination, the resin film of present embodiment can show Go out high-fire resistance.
And it can consider that the half ester in formula (5) contains carboxyl, thus can realize when preparing photosensitive polymer combination The raising of sensitivity.
Furthermore it is also possible to replace above-mentioned maleic acid using the unsaturated carboxylic acid anhydrides that other intramoleculars have cyclic structure Acid anhydride.
(in formula (5), R is the atomic group from phenolic resin.)
Furthermore it is possible to think that the resin combination of present embodiment provides the half ester shown in formula (5) as described above.Thus table Reveal the effect of heat resistance etc., therefore by being heated etc. before various uses is supplied in resin combination, Neng Gouzeng Plus the containing ratio for stating half ester.
Scope as the condition of the heating, for example, 50~100 DEG C.
Also, such as in the case of the purposes in for technique by heating process etc., additionally it is possible to by above-mentioned phenolic aldehyde tree Fat is used in mixed way without being supplied in heating at normal temperatures with polymer.
In the heating, from the viewpoint of reaction is promoted, catalyst can be properly added, such as base catalysis can be added Agent or acid catalyst.
As base catalyst, the hydroxy compounds such as sodium hydroxide, potassium hydroxide, the alkyl such as pyridine or triethylamine can be used The metal salts, ammonia etc. such as the amine compounds such as amine, dimethylaniline, methenamine, dimethyl aminopyridine, sodium acetate.They can be single Solely using one kind, in order to further improve reactivity, two or more base catalysts can also be combined.
In addition, as acid catalyst, the organic acids such as inorganic acid, the p-methyl benzenesulfonic acid such as sulfuric acid or hydrochloric acid, fluorination can be used Lewis acids such as borate ether etc..
Furthermore it is also possible to replace above-mentioned maleic acid using the unsaturated carboxylic acid anhydrides that other intramoleculars have cyclic structure Acid anhydride.
Also, the resin combination of present embodiment can include the polymerization containing the repetitive unit shown in above-mentioned formula (1) The acid anhydrides position of thing forms the ester compounds of ester bond with the phenolic hydroxyl group that phenolic resin possesses.In this case, this embodiment party In the resin combination of formula, the acid anhydrides (such as maleic anhydride) of the polymer can whole open loops, and/or phenolic resin possessed Phenolic hydroxyl group can have ester bond.Thereby, it is possible to further improve heat resistance.
[photosensitive polymer combination]
As the more specifically purposes on above-mentioned resin combination, conduct photoresist as follows can be enumerated The purposes of composition.
The photosensitive polymer combination of present embodiment can include above-mentioned phenolic resin, containing shown in above-mentioned formula (1) The polymer and emulsion of repetitive unit.That is, the photosensitive polymer combination of present embodiment can include above-mentioned resin combination Thing and emulsion.
Here, on the phenolic resin and polymer that are used in the photosensitive polymer combination of present embodiment, can Using material same as described above.Hereinafter, component in addition is illustrated.
(emulsion)
The photosensitive polymer combination of present embodiment includes emulsion.
As the emulsion, such as diazonium naphtoquinone compounds, diaryl group iodized salt, triarylsulfonium salt or sulfonium-boron can be used The salt such as hydrochlorate, 2- nitrobenzyls ester compounds, N- iminosulfonates compound, acid imide sulfonate compound, 2,6- are double (trichloromethyl) -1,3,5- triaizine compounds or dihydropyridine compound.Wherein, particularly preferably dissolved using sensitivity and solvent The excellent diazonium naphtoquinone compounds of property.As diazonium naphtoquinone compounds, such as compound shown below can be used.
(n2 is less than more than 15 integer.)
In each compound more than, Q is any one or hydrogen atom in the structure shown in following (a)~(c).Its In, at least one structure for shown in following (a)~(c) in the Q of each compound any one.
In the present embodiment, as diazonium naphtoquinone compounds, such as phenolic compounds and 1,2- naphthoquinones -2- two are more preferably used The ester of two nitrine -4- sulfonic acid of nitrine -5- sulfonic acid or 1,2- naphthoquinones -2-.
The photosensitive polymer combination of present embodiment can be so-called eurymeric, it is believed that residue in unexposed portion Heat of emulsion when curing in relief pattern produces acid decomposing, which also plays as reaction promoter Important function.As the diazonium naphtoquinone compounds with such effect, particularly preferably using 1, the 2- naphthalenes for being easier to be thermally decomposed The ester of two nitrine -4- sulfonic acid of quinone -2-.
The content of emulsion in the photosensitive polymer combination of present embodiment is not particularly limited, relative to phenolic aldehyde tree 100 mass parts of fat are preferably more than 5 mass parts, more preferably more than 8 mass parts.Also, the sense in photosensitive polymer combination The content of photo etching is preferably 80 below mass part relative to 100 mass parts of phenolic resin, and more preferably 60 is below mass part.Pass through The content of emulsion within the above range, can play good patterning performance.
(solvent)
Resin combination and photosensitive polymer combination described in present embodiment can be by molten by above-mentioned each component Solution is used with varnish shape in a solvent.
As the example of this solvent, N- methyl -2- Pyrrolizidines ketone, gamma-butyrolacton, N, N- dimethylacetamides can be enumerated Amine, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, propylene glycol monomethyl ether, dipropyl Glycol monomethyl ether, propylene glycol methyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl isophthalic acid, 3- butanediol acetic acid Ester, 1,3 butylene glycol -3- monomethyl ethers, methyl pyruvate, ethyl pyruvate and methyl -3- methoxy propyl acid esters etc..
In addition, from significantly inhibit resin film produce cracking from the viewpoint of, in these compounds, preferably using selected from Gamma-butyrolacton, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, propane diols list first Compound in ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate.
The content of solvent in the resin combination and photosensitive polymer combination of present embodiment is not particularly limited, phase It is preferably more than 100 mass parts, more preferably more than 150 mass parts for 100 mass parts of phenolic resin.
Also, the content of the solvent in the resin combination and photosensitive polymer combination of present embodiment is relative to phenolic aldehyde 100 mass parts of resin are preferably 1000 below mass part, and more preferably 800 is below mass part.The content of solvent is in above range When interior, appropriate operability can be brought.
(other compositions)
The resin combination and photosensitive polymer combination of present embodiment are in addition to coordinating mentioned component, additionally it is possible to root Coordinate various composition according to purposes.
For example, as alkali soluble resin, it can in addition coordinate phenolic resin, phenol aralkyl resin, hydroxy styrenes The acrylic resins such as resin, methacrylic resin, methacrylate resin, cyclic olefin resinoid etc..
Further, it is also possible to be added as needed on antioxidant, filler, silane coupling agent, surfactant, closely sealed auxiliary agent, The additive such as end-capping reagent and sensitizer.
In addition, their additive amount is arbitrary.
(purposes)
The resin combination and photosensitive polymer combination of present embodiment can be used in forming resist or permanent film etc. Resin film.From the viewpoint of heat resistance, preferably such purposes.
Also, above-mentioned resist is coated with for example by using the methods of spin coating, roller coat, flow coat, dip-coating, spraying, blade coating Photosensitive polymer combination and the resin film composition that solvent is removed and is obtained.
Above-mentioned permanent film is by by the way that above-mentioned resin film is exposed and is developed, after patterned required shape, utilizing heat The cured film that processing etc. cures it and obtains is formed.Permanent film is such as available for protective film, interlayer film or padded coaming.
Then, to applying the resin combination of present embodiment or the electronic device 100 of photosensitive polymer combination An example illustrates.
The electronic device 100 of present embodiment can possess above-mentioned resin film.
Electronic device 100 shown in Fig. 1 is, for example, semiconductor chip.In this case, such as by by electronic device 100 It is mounted in via convex block 52 on wiring substrate, obtains semiconductor package body.Electronic device 100, which possesses, to be provided with transistor etc. and partly leads The semiconductor substrate of volume elements part and the multilayer wired layer (not shown) set on a semiconductor substrate.In multilayer wired layer most The superiors' distribution 34 that upper strata is provided with interlayer dielectric 30 and is set on interlayer dielectric 30.The superiors' distribution 34 for example by Aluminium is formed.Also, on interlayer dielectric 30 and it is provided with passivating film 32 on the superiors' distribution 34.In a part for passivating film 32 It is provided with the opening that the superiors' distribution 34 exposes.
Wiring layer 40 again are provided with passivating film 32.Wiring layer 40 has the insulating layer being arranged on passivating film 32 again 42nd, the distribution again 46 that is arranged on insulating layer 42 and it is arranged on insulating layer 42 and the insulating layer 44 on distribution 46 again.Insulation Layer 42 is formed with the opening being connected with the superiors distribution 34.Again distribution 46 be formed on insulating layer 42 and insulating layer 42 set by In opening, it is connected with the superiors distribution 34.The opening that insulating layer 44 is provided with distribution 46 is connected again.
In the present embodiment, can be by by being solidified to form above-mentioned resin combination or photosensitive polymer combination Resin film form more than one in passivating film 32, insulating layer 42 and insulating layer 44.In this case, such as to by photonasty The coated film that resin combination is formed exposes ultraviolet and is developed and patterned, and afterwards, is heating and curing to it, thus Form passivating film 32, insulating layer 42 or insulating layer 44.
In the opening set by insulating layer 44, such as across UBM (Under Bump Metallurgy：It is golden under convex block Belong to) the formation convex block 52 of layer 50.Electronic device 100 is connected such as via convex block 52 with wiring substrate.
In addition, the present invention is not limited to the above embodiment, it can realize the deformation in the range of the object of the invention, change It is good etc. to be included in the invention.
Hereinafter, it is attached the example of reference mode.
1. a kind of resin combination, it includes novolak phenolics and contain the repetition list shown in following formula (6) The polymer of member.
2. the resin combination according to 1., wherein, the weight average molecular weight of above-mentioned novolak phenolics is 300 Below the above 20000.
3. according to the resin combination described in 1. or 2., it includes the acid anhydrides for possessing the repetitive unit shown in above-mentioned formula (6) The compound that position is bonded with the phenolic hydroxyl group that above-mentioned novolak phenolics possess via ester bond.
4. the resin combination according to any one of 1. to 3., wherein, above-mentioned polymer also contains with following formula (2) institute The repetitive unit or the repetitive unit shown in following formula (3) shown.
(in formula (2), R1、R2、R3And R4It is separately hydrogen or the organic group of carbon number 1~30；N for 0,1 or 2。)
(in formula (3), Ra is separately the organic group of carbon number 1~30.M is less than more than 05 integer.)
5. a kind of photosensitive polymer combination, it includes novolak phenolics, contain the weight shown in following formula (6) The polymer and emulsion of multiple unit.
6. the photosensitive polymer combination according to 5., wherein, above-mentioned emulsion is diazonium naphtoquinone compounds.
7. according to the photosensitive polymer combination described in 5. or 6., wherein, the weight of above-mentioned novolak phenolics is equal Molecular weight is less than more than 300 20000.
8. the photosensitive polymer combination according to any one of 5. to 7., it includes possess shown in above-mentioned formula (6) What the acid anhydrides position of repetitive unit was bonded with the phenolic hydroxyl group that above-mentioned novolak phenolics possess via ester bond Compound.
9. the photosensitive polymer combination according to any one of 5. to 8., wherein, above-mentioned polymer is also containing following Repetitive unit shown in formula (2) or the repetitive unit shown in following formula (3).
(in formula (2), R1、R2、R3And R4It is separately hydrogen or the organic group of carbon number 1~30.N for 0,1 or 2。)
(in formula (3), Ra is separately the organic group of carbon number 1~30.M is less than more than 05 integer.)
10. the resin film that a kind of solidfied material of photosensitive polymer combination by any one of 5. to 9. is formed.
A kind of 11. electronic device for possessing the resin film described in 10..
Embodiment
Then, the embodiment of the present invention is illustrated.
First, on each material used in embodiment, preparation is proceeded as described below.
(novolak phenolics 1)
Possess agitating device, thermometer, heat exchanger 3L four-hole boiling flask in, relative to metacresol and paracresol with Molar ratio (metacresol:Paracresol)=5:1000 parts of the phenols that 5 ratio mixes, adds 37% formlinata aquae concentratac 526 parts (molar ratio=0.70 of formaldehyde/phenol), 10 parts of oxalic acid, react when progress 6 is small under reflux.Afterwards, carry out under normal pressure Dehydration is warming up to 230 DEG C of progress decompression dehydrations up to interior 170 DEG C of temperature under the decompression of 8.0kPa, obtains weight average molecular weight 11, 000th, 1050 parts of the novolak phenolics of dispersion degree 9.0, unreacted phenols 0.5%.
(polymer 1)
Possess mixer, cooling tube appropriate size reaction vessel in, weigh maleic anhydride (735g, 7.5mol), 2- norbornene (706g, 7.5mol) and double (2 Methylpropionic acid) dimethyl esters (69g, 0.3mol) of 2,2'- azo, and it is dissolved in first In base ethyl ketone and toluene.To the lysate, after by nitrogen bubbling, the dissolved oxygen in system is removed, stir while 60 DEG C, 15 it is small when under conditions of implement heat treatment.Thus, the copolymer of 2- norbornene and maleic anhydride is obtained.Then, using big After amount methanol makes the above-mentioned lysate reprecipitation that is cooled to room temperature, precipitate is filtered, makes its drying using vacuum drier, obtains The white solid of 1100g.
The weight average molecular weight (Mw) of the polymer obtained in this way is 10,000, and dispersion degree (Mw/Mn) is 2.1.
(polymer 2)
Prepare the copolymer SMA-1000-P (production of Cray Valley USA, LLC companies) of phenylethylene/maleic anhydride.It is poly- The weight average molecular weight (Mw) of compound is 3,600, and dispersion degree (Mw/Mn) is 2.3.
(polymer 3)
Possess mixer, cooling tube appropriate size reaction vessel in, weigh indenes (870g, 7.5mol) and 2,2'- Double (2 Methylpropionic acid) dimethyl esters (11.5g, 0.05mol) of azo, and be dissolved in methyl ethyl ketone.To the lysate, pass through After nitrogen bubbling removes the dissolved oxygen in system, stir on one side, while reach after 70 DEG C lasted from each mouth 5 it is small when progressively add Add maleic anhydride (735g, 7.5mol) methyl ethyl ketone solution, n-dodecyl mercaptan (20.2g, 0.10mol) methyl ethyl ketone Solution, is heat-treated when further implementation 2 is small afterwards.Thus, the copolymer of indenes and maleic anhydride is obtained.
(polymer 4)
Possess mixer, cooling tube appropriate size reaction vessel in, weigh indenes (870g, 7.5mol) and 2,2'- Double (2 Methylpropionic acid) dimethyl esters (23.0g, 0.1mol) of azo, and be dissolved in methyl ethyl ketone.To the lysate, pass through nitrogen Bubbling by system dissolved oxygen remove after, on one side stir, while reach lasted after 75 DEG C 6 it is small when progressively add citraconic anhydride (840g, 7.5mol) methyl ethyl ketone solution, is heat-treated when further implementation 3 is small afterwards.Thus, indenes and citraconic anhydride are obtained Copolymer.
(polymer 5)
Possess mixer, cooling tube appropriate size reaction vessel in, weigh indenes (870g, 7.5mol) and 2,2'- Double (2 Methylpropionic acid) dimethyl esters (11.5g, 0.05mol) of azo, and be dissolved in methyl ethyl ketone.To the lysate, pass through After nitrogen bubbling removes the dissolved oxygen in system, stir on one side, while reach after 70 DEG C lasted from each mouth 5 it is small when progressively add Add the methyl ethyl ketone solution, just for being mixed with maleic anhydride (662g, 6.75mol) and maleimide (72.8g, 0.75mol) Lauryl mercaptan (20.2g, 0.10mol) methyl ethyl ketone solution, is heat-treated when further implementation 2 is small afterwards.Thus, obtain Indenes and maleic anhydride, the copolymer of maleimide.
(polymer 6)
Possess mixer, cooling tube appropriate size reaction vessel in, weigh indenes (696g, 6.0mol), 2- drop ice Piece alkene (141g, 1.5mol) and double (2 Methylpropionic acid) dimethyl esters (11.5g, 0.05mol) of 2,2'- azo, and it is dissolved in methyl In ethyl ketone.To the lysate, after by nitrogen bubbling, the dissolved oxygen in system is removed, while stirring, while reaching 70 DEG C Lasted afterwards from each mouth 7 it is small when progressively add maleic anhydride (735g, 7.5mol) methyl ethyl ketone solution, n-dodecyl mercaptan (20.2g, 0.10mol) methyl ethyl ketone solution, is heat-treated when further implementation 5 is small afterwards.Thus, indenes, norbornene are obtained With the copolymer of maleic anhydride.
(phenolic compounds 1)
Prepare with phenolic compounds shown in following formula (Honshu Chemical Co., Ltd. produces, product name TrisP-PA).
(emulsion 1)
Prepare with the emulsion shown in following formula (B-1) (DAITO CHEMIX Co., Ltd.s produce, product name PA-28).
Wherein, the Q in formula (B-1) represents that 90% is above-mentioned formula (B- in whole Q for hydrogen atom or by above-mentioned formula (B-2) 2)。
(surfactant 1)
Prepare fluorine system surfactant MEGAFACE F-556 (Dainippon Ink Chemicals's production).
[preparation of photosensitive polymer combination]
On each embodiment and each comparative example, prepare each raw material of the amount shown in Tables 1 and 2, be dissolved in PGMEA (the third two Alcohol methyl ether acetate) in, afterwards, filtered using the fluororesin filter that aperture is 0.2 μm, obtain photoresist Composition.
In addition, when preparing the photosensitive polymer combination of each embodiment and each comparative example, PGMEA (propane diols lists are adjusted Methyl ether acetate) so that the content (summations of novolak phenolics and polymer or phenolic compounds) of resin component reaches 25%.
In addition, in embodiments, on Examples 1 and 2, in novolak phenolics and the methyl of polymer 1 Further addition methyl ethyl ketone, then add 5 mass parts of pyridine in ethyl ketone solution, after being heated 2 days with 70 DEG C, removal solvent, After pyridine, prepared using filter filtering.
It is also, molten in the methyl ethyl ketone of novolak phenolics and 3 solution of polymer on embodiment 6~11 Methyl ethyl ketone, 5 mass parts of pyridine are further added in liquid, after being reacted 3 days with 70 DEG C, remove reaction dissolvent, pyridine.
On embodiment 13,14,15, novolak phenolics and polymer solution 4 corresponding with each embodiment, 5th, in 6, methyl ethyl ketone, 5 mass parts of pyridine are further added, after being reacted 3 days with 70 DEG C, remove reaction dissolvent, pyridine.
In addition, on embodiment 3~5,12, comparative example 1~2, it is different from above-described embodiment 1~2,6~11,13~15, Each dissolution of raw material is set not make novolak phenolics and polymer reaction before PGMEA.
The photosensitive polymer combination obtained as described above is evaluated according to following items.
(sensitivity)
Photosensitive polymer combination obtained above is respectively coated on 4 inches of silicon wafer using spin coater, afterwards, Using heating plate with 110 DEG C of prebake conditions 2 minutes, the coat film of about 2 μm of thickness is obtained.To the coat film, pass through letterpress strain Mask (the test chart No.1 of formula commercial firm production：Describing has the residual pattern and pierced pattern of 0.88~50 μm of width), use i lines Exposure machine (Nikon Corp. produces, NSR-4425i) changes light exposure and is irradiated.
Then, the tetramethylammonium hydroxide aqueous solution using 2.38% causes prebake conditions as developer solution, adjusting developing time The difference of thickness after rear thickness and development reaches 1.0 μm, carries out immersion development twice, thus dissolves exposure portion and removes, it Pure water rinsing is utilized afterwards 10 seconds.The value of lowest exposure amount formed with 100 μm of square through-hole pattern is evaluated as feeling Luminosity.The results are shown in Tables 1 and 2.
(Evaluation of Heat Tolerance)
Photosensitive polymer combination obtained above is respectively coated on 4 inches of silicon wafer using spin coater, afterwards, Using heating plate with 110 DEG C of prebake conditions 2 minutes, the coat film of about 2 μm of thickness is obtained.To the coat film, pass through letterpress strain The mask (residual pattern of 1mm) of formula commercial firm production, the Mask Aligner produced using SUSS MicroTec companies MA8, will be fixed as being exposed for 40 seconds the time for exposure.Then, by being immersed in 2.38% tetramethylammonium hydroxide aqueous solution, Exposure portion is dissolved and is removed, utilizes pure water rinsing 30 seconds afterwards.At this time, the film decrement in unexposed portion is about 0.02 μm.Close Unexposed portion after above-mentioned carry out pattern processing, is dried with the condition of 100 DEG C, 1 minute, obtains resin film.
On the resin film, heated with the condition of 140 DEG C, 3 minutes, using metallurgical microscopes, observe resin Whether the shape of film changes.In addition, the metewand in this experiment is as follows.The results are shown in Tables 1 and 2.
◎：Not it was observed that the change in shape of pattern.
○：Although deformation slightly, the level having no problem in practical application are able to observe that in the corner of pattern.
×：It was observed that the change in shape of pattern.
[table 1]
[table 2]
As shown in Table 1 and Table 2, in embodiments, the resin film of high temperature has been obtained being resistant to.Also, each embodiment In obtained various photosensitive polymer combinations sensitivity it is also high, be identified that the serviceability as photoresist is high.
In addition, in each embodiment, on embodiment 1 and embodiment 4, even if confirming the condition of heat-resistance test being changed to 150 DEG C, the condition of 3 minutes, also can fully keep pattern form.
In addition, the photosensitive polymer combination on the present embodiment shows high heat resistance, it is believed that it is resistance to show this One of the reason for hot, is novolak phenolics with having the unsaturated carboxylic acid anhydrides list of cyclic structure containing intramolecular The specific polymer of member is crosslinked securely by ester bond.
The FT-IR spectrums (Fig. 2 (a)) of above-mentioned polymer 2 and the FT-IR spectrums (Fig. 2 (b)) of following composition are represented in fig. 2, Said composition is with 25 by polymer 2 and novolak phenolics:75 ratio solvent is in methyl ethyl ketone, in pyridine In the presence of reacted 1 day with 70 DEG C, remove solvent, the composition obtained after pyridine afterwards.From Fig. 2 (a) compared with Fig. 2 (b), In Fig. 2 (b), in 1700cm specific to ester bond- 1Nearby observe absworption peak.
I.e., in the present invention, prompted this phenolic resin that there is the unsaturated carboxylic acid anhydrides list of cyclic structure with intramolecular The key of member contributes to heat resistance.
Industrial applicability
Interaction of the resin combination of the present invention based on phenolic resin with the polymer with specific construction unit, Can show high-fire resistance, such as when photosensitive polymer combination is made, can balance show well it is excellent Sensitivity and high-fire resistance.
Also, the resin combination of the present invention is in the purposes in addition to this photosensitive polymer combination, additionally it is possible to It is suitably applied to require the purposes of heat resistance.
This application claims the priority based on the Japanese Patent Application 2015-163438 proposed in Japan on the 21st of August in 2015, And its entire disclosure is incorporated in this.

Claims (10)

  1. A kind of 1. resin combination, it is characterised in that：
    Comprising phenolic resin and containing with the polymer of the repetitive unit shown in following formula (1),
    In formula (1), RX、RYSeparately represent the organic group of hydrogen or carbon number 1~3.
  2. 2. resin combination according to claim 1, it is characterised in that：
    The weight average molecular weight of the phenolic resin is less than more than 300 20000.
  3. 3. resin combination according to claim 1 or 2, it is characterised in that：
    Passed through comprising the acid anhydrides position for possessing the repetitive unit shown in the formula (1) and the phenolic hydroxyl group that the phenolic resin possesses The compound formed by ester bond bonding.
  4. 4. resin combination according to any one of claim 1 to 3, it is characterised in that：
    The polymer, which also contains, to be selected from the unit from norbornene-type monomers shown in following formula (2), the source shown in formula (3) Maleimide is derived from shown in unit from indene monomer and formula (8) shown in unit, formula (7) from styrene monomer At least one unit in the unit of class monomer,
    In formula (2), R1、R2、R3And R4It is separately hydrogen or the organic group of carbon number 1~30, n 0,1 or 2,
    In formula (3), Ra is separately the organic group of carbon number 1~30, and m is less than more than 05 integer,
    In formula (7), R5To R11It is separately hydrogen or the organic group of carbon number 1~3,
    In formula (8), R12It independently is the organic group of hydrogen or carbon number 1~10.
  5. A kind of 5. resin combination, it is characterised in that：
    The phenol hydroxyl that acid anhydrides position comprising the polymer containing the repetitive unit shown in following formula (1) possesses with phenolic resin Base forms the ester compounds of ester bond,
    In formula (1), RX、RYSeparately represent the organic group of hydrogen or carbon number 1~3.
  6. A kind of 6. photosensitive polymer combination, it is characterised in that：
    Include the resin combination and emulsion any one of claim 1 to 5.
  7. 7. photosensitive polymer combination according to claim 6, it is characterised in that：
    The emulsion is diazonium naphtoquinone compounds.
  8. A kind of 8. resin film of the resin combination including any one of claim 1 to 5.
  9. A kind of 9. resin film of the photosensitive polymer combination including described in claim 6 or 7.
  10. A kind of 10. electronic device for possessing the resin film described in claim 8 or 9.
CN201680048062.7A 2015-08-21 2016-07-21 Resin combination, photosensitive polymer combination, resin film and electronic device Pending CN107922708A (en)

Applications Claiming Priority (3)

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JP2015163438 2015-08-21
JP2015-163438 2015-08-21
PCT/JP2016/071401 WO2017033633A1 (en) 2015-08-21 2016-07-21 Resin composition, photosensitive resin composition, resin film and electronic device

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110511532A (en) * 2019-09-25 2019-11-29 河南工业大学 A kind of maleic anhydride-acrylate copolymer modified phenolic resin
CN113811556A (en) * 2019-05-08 2021-12-17 住友电木株式会社 Photosensitive resin composition, resin film, and electronic device

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018061584A1 (en) * 2016-09-28 2018-04-05 住友ベークライト株式会社 Phenol resin composition for friction material and friction material
JP7088640B2 (en) * 2017-08-01 2022-06-21 旭化成株式会社 Semiconductor devices and their manufacturing methods
JP7043756B2 (en) * 2017-08-31 2022-03-30 住友ベークライト株式会社 Photosensitive resin composition, pattern forming method, electronic device manufacturing method, polymer and polymer manufacturing method
JP7020018B2 (en) * 2017-09-15 2022-02-16 住友ベークライト株式会社 Rubber composition
JP6764885B2 (en) * 2018-01-11 2020-10-07 Ｊｆｅケミカル株式会社 Thermosetting resin composition and its cured product
JP6950573B2 (en) * 2018-02-26 2021-10-13 Jnc株式会社 Thermosetting composition
JP7559421B2 (en) 2020-03-02 2024-10-02 住友ベークライト株式会社 Polymer solution for forming color filters or black matrices
WO2022065225A1 (en) * 2020-09-23 2022-03-31 住友ベークライト株式会社 Polymer, polymer solution, and photosensitive resin composition

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6416925B1 (en) * 1997-02-18 2002-07-09 Fuji Photo Film Co., Ltd. Positive working photosensitive composition
US6534235B1 (en) * 2000-10-31 2003-03-18 Kansai Research Institute, Inc. Photosensitive resin composition and process for forming pattern
CN1500119A (en) * 2001-02-26 2004-05-26 音思万有限公司 Positive photodefinable compsn. of polycarboxylic acid, phenolic and thermocurable resins
CN103370347A (en) * 2010-11-24 2013-10-23 普罗米鲁斯有限责任公司 A self-imageable film forming polymer, compositions thereof and devices and structures made therefrom
CN104216222A (en) * 2013-05-29 2014-12-17 住友电木株式会社 Photosensitive resin composition and electronic device
CN104216228A (en) * 2013-05-29 2014-12-17 住友电木株式会社 Negative photosensitive resin composition, electronic device and polymer
JP5672403B1 (en) * 2014-05-26 2015-02-18 住友ベークライト株式会社 Photosensitive resin composition and electronic device

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS595243A (en) * 1982-07-02 1984-01-12 Hitachi Ltd Radiation sensitive composition and formation of pattern
US5110700A (en) * 1990-12-28 1992-05-05 Xerox Corporation Electrophotographic imaging member
JPH06305076A (en) * 1993-04-26 1994-11-01 Hitachi Chem Co Ltd Production of metal base melamine resin decorative panel
JP3429852B2 (en) * 1993-06-04 2003-07-28 シップレーカンパニー エル エル シー Negative photosensitive composition
EP0805825B1 (en) * 1995-01-27 2000-08-23 TYCO Electronics Corporation Gels from anhydride-containing polymers
JP3944966B2 (en) * 1996-09-30 2007-07-18 日本ゼオン株式会社 Modified norbornene polymer and method for producing the same
JP2000122278A (en) * 1998-10-21 2000-04-28 Okamoto Kagaku Kogyo Kk Photosensitive composition and photosensitive planographic printing plate
JP3615981B2 (en) * 1999-11-24 2005-02-02 クラリアント インターナショナル リミテッド Photosensitive resin composition
US6449918B1 (en) 1999-11-08 2002-09-17 Premark Rwp Holdings, Inc. Multipanel floor system panel connector with seal
CN1717630A (en) * 2003-06-30 2006-01-04 株式会社新克 Positive photosensitive composition
JP2005105209A (en) 2003-10-01 2005-04-21 Yokohama Rubber Co Ltd:The Highly damping elastomer composition
JP4951200B2 (en) * 2004-08-20 2012-06-13 東洋インキＳｃホールディングス株式会社 Color filter
JP2015166431A (en) * 2014-03-04 2015-09-24 日立化成株式会社 Thermosetting resin composition, prepreg and laminated plate
JP6287652B2 (en) * 2014-07-10 2018-03-07 日油株式会社 Photosensitive resin composition and use thereof
JP6528421B2 (en) * 2015-01-28 2019-06-12 住友ベークライト株式会社 Photosensitive resin composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6416925B1 (en) * 1997-02-18 2002-07-09 Fuji Photo Film Co., Ltd. Positive working photosensitive composition
US6534235B1 (en) * 2000-10-31 2003-03-18 Kansai Research Institute, Inc. Photosensitive resin composition and process for forming pattern
CN1500119A (en) * 2001-02-26 2004-05-26 音思万有限公司 Positive photodefinable compsn. of polycarboxylic acid, phenolic and thermocurable resins
CN103370347A (en) * 2010-11-24 2013-10-23 普罗米鲁斯有限责任公司 A self-imageable film forming polymer, compositions thereof and devices and structures made therefrom
CN104216222A (en) * 2013-05-29 2014-12-17 住友电木株式会社 Photosensitive resin composition and electronic device
CN104216228A (en) * 2013-05-29 2014-12-17 住友电木株式会社 Negative photosensitive resin composition, electronic device and polymer
JP5672403B1 (en) * 2014-05-26 2015-02-18 住友ベークライト株式会社 Photosensitive resin composition and electronic device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
俞铁铭 等: "《精细有机单元反应与工艺》", 31 January 2015, 浙江大学出版社 *
段行信: "《实用精细有机合成手册》", 31 January 2000, 化学工业出版社 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113811556A (en) * 2019-05-08 2021-12-17 住友电木株式会社 Photosensitive resin composition, resin film, and electronic device
CN113811556B (en) * 2019-05-08 2024-05-28 住友电木株式会社 Photosensitive resin composition, resin film and electronic device
CN110511532A (en) * 2019-09-25 2019-11-29 河南工业大学 A kind of maleic anhydride-acrylate copolymer modified phenolic resin
CN110511532B (en) * 2019-09-25 2022-03-25 河南工业大学 A kind of maleic anhydride-acrylate copolymer modified phenolic resin

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