CN108586748A - A kind of benzocyclobutene functionalization organosilicon polymer and its preparation method and application - Google Patents
A kind of benzocyclobutene functionalization organosilicon polymer and its preparation method and application Download PDFInfo
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- CN108586748A CN108586748A CN201810364065.2A CN201810364065A CN108586748A CN 108586748 A CN108586748 A CN 108586748A CN 201810364065 A CN201810364065 A CN 201810364065A CN 108586748 A CN108586748 A CN 108586748A
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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Abstract
The invention belongs to high performance resin technical fields, the specially organosilicon polymer and its preparation method and application of the functional group containing benzocyclobutene.Organosilicon polymer of the present invention is obtained by one or more kinds of siloxanes hydrolytic condensations.The material has good lithography performance, in the broad prospect of application that Electronic Packaging, photoelectric device, integrated circuit fields have.It can directly be applied, can also be modified by the way that other organic and inorganic modifying agent are added.It is such as used as encapsulating material, is applied to electronic devices or the photoelectric devices such as solar cell, display device, LED, MEMS.Also be used as optical device or optical film materials, be alternatively arranged as semiconductor, integrated circuit fields low dielectric layer between dielectric material, low dielectric lithography glue etc..It can be also used for the preparation of high-property resin composite material.
Description
Technical field
The invention belongs to high performance resin technical fields, and in particular to the organic siliconresin of the functional group containing benzocyclobutene and
Preparation method and application.
Background technology
Benzocyclobutene is a kind of outstanding polymer material, and ring-opening polymerisation can occur after heating, generates high crosslinking, resistance to height
The low dielectric polymer material of temperature.DOW Chemical develops a series of CYCLOTENE Advanced Electronics
The photoresist of Resins is all based on the preparation of DVS-BCB performed polymers.DVS-BCB is logical using DVS and 4- bromine benzocyclobutenes
Cross small molecule prepared by Heck reactions.Photoresist based on DVS-BCB is typically that DVS-BCB obtains certain molecular weight by pre-polymerization
Then the performed polymer of size is added photosensitizer and configures.The control of pre-polymerization condition is an important factor.Based on DVS-BCB
Photoresist have excellent thermal stability, dielectric constant is small, 1MHz at be 2.65.However, its coefficient of thermal expansion or phase
To bigger, have its coefficient of thermal expansion of data report be 62 μm/(m ×oC).It needs to develop novel heat safe photoresist.
Invention content
The purpose of the present invention is to provide one kind to have excellent performance, it is poly- to prepare the convenient functionalized organosilicon of benzocyclobutene
Close object and its preparation method and application.
Benzocyclobutene provided by the invention（BCB）Functionalized organosilicon polymer is by one or more kinds of silica
Alkane hydrolytic condensation and obtain, structural formula is as follows：
Wherein, R1, R2, R3It is respectively selected from methyl, ethyl, propyl, allyl, isopropyl, cyclohexyl, phenyl, hydrogen atom, carbon carbon
Double bond, hydroxypropyl, chloropropyl, aminopropyl etc.；M, n round numbers；Wherein m is more than 2, preferably 3 ~ 100；N is more than or equal to 0, preferably
For 1-100.
In the present invention, the functionalized organosilicon polymers of BCB wherein at least include the functionalized organosilicon M of BCB, knot
Structure formula is as follows：
R4 is methoxyl group, ethyoxyl or isopropoxy etc..
The following one kind of typical organosilicon M molecular formula：
。
In the present invention, in addition to organosilicon M, other siloxanyl monomers can be dimethoxydiphenylsilane, diphenyl two
Ethoxysilane, dimethyl diethoxysilane, diethyldiethoxysilane, aminomethyl phenyl diethoxy silane or chloromethyl
Methyl dimethoxysilane etc..
In the present invention, the organosilicon M be with double bond siloxanes and 4- bromines benzocyclobutene pass through Heck reaction system
It is standby to obtain.If M1 is to react to prepare by Heck by methylvinyldimethoxysilane and 4- bromines benzocyclobutene.This
Kind reaction needs in an inert atmosphere（N2, Ar gas）Carry out, the solvent of this Heck reaction is dry solvent, can be selected toluene,
Tetrahydrofuran, 2- methyltetrahydrofurans, acetonitrile, dioxane, n,N-Dimethylformamide, n,N-dimethylacetamide etc..It urges
Palladium, four can be selected in agent（Triphenylphosphine）Palladium, palladium carbon, diphenylphosphine ferrocene palladium chloride, tetra-triphenylphosphine palladium, dichloro
Two triphenylphosphine palladiums, palladium carbon etc..Ligand selects triphenylphosphine or three（O-tolyl）Phosphine, Alkali absorption agent can be selected triethylamine,
Potassium carbonate, sodium carbonate, cesium carbonate, pyridine, imidazoles etc..Reaction temperature 50 ~ 150oC, reaction time 2h ~ 48h, preferably 3h ~
12h。
After reaction, precipitation, filter cake nonpolar solvent are filtered by modes such as suction filtrations（Such as toluene, hexamethylene, oil
Ether etc.）Washing, merging filtrate, concentrated by rotary evaporation.Concentrate obtains monomer M through oil pump vacuum distillation purification.
In the present invention, M monomer synthetic polymers are carried out by the hydrolysis-condensation reaction under acid or base catalyst effect.
Can be tetramethylammonium hydroxide when catalyst is alkali（Aqueous solution or ethanol solution）, can also be alkali glue（Utilize hydrogen-oxygen
Change potassium and is prepared by organosilicon reaction）Deng.Can be formic acid, acetic acid, methanesulfonic acid etc. when catalyst is acid.
The siloxanyl monomers of other cohydrolysis can be dimethoxydiphenylsilane, diphenyl diethoxy silane, two
Methyldiethoxysilane, diethyldiethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, benzene
Ethyl triethoxy silicane alkane, methyl orthosilicate, ethyl orthosilicate etc..
Other end-capping reagents, typically small-molecular-weight list siloxanes are added when necessary, such as trimethylethoxysilane, trimethyl
Methoxy silane, diphenylmethylethoxysilane, triphenyl Ethoxysilane, triphenylmethoxy silane, dimethylvinylsiloxy
Base oxethyl silane, dimethylvinylmethoxysiiane, dimethylethoxysilane, dimethyl methoxy silane etc.；Also may be used
To be disiloxane, such as hexamethyldisiloxane（MM）, tetramethyl divinyl disiloxane, 1,3- dimethyl -1,1,3,3-
Four ethylene disiloxane, 1,1,3,3- tetramethyl -1,3- diphenyl disiloxane, 1,3- divinyl -1,3- dimethyl -1,3-
Diphenyl disiloxane, tetramethyl disiloxane, decamethyl tetrasiloxane etc..
Other solvents can be added in heretofore described hydrolysis-condensation reaction, can be alkane solvent（Petroleum ether, just
Hexane, hexamethylene, normal heptane, normal octane, etc.）, anhydrous tetrahydro furan, water, toluene, benzene, dimethylbenzene, dioxane, methyl four
One or more of hydrogen furans, dichloromethane, dimethyl-tetrahydrofuran, glycol dimethyl ether, ethylene glycol diethyl ether etc..
Heretofore described hydrolysis-condensation reaction can first use simple reflux, after use instead reflux band water installations,
Hydrolysis-condensation reaction is set fully to carry out；Simple reflux can also first be used, after use normal pressure or vacuum distillation apparatus instead, make anti-
It should fully carry out；Reflux band water installations or distilling apparatus can also directly be used（Normal pressure or decompression）.
Hydrolysis-condensation reaction of the present invention, range of reaction temperature be room temperature to 120 DEG C, temperature programmed control can be used；
Such as first react at room temperature, after heat up.
Hydrolysis-condensation reaction of the present invention, reaction time are 1 ~ 24 hour.
Hydrolysis-condensation reaction of the present invention if catalyst is tetramethylammonium hydroxide, can pass through liter after reaction
Temperature decomposes to 130~160 DEG C and removes catalyst；Also petroleum ether, dichloromethane, ethyl acetate, butyl acetate etc. can be added, into
One step carries out pickling（Remove basic catalyst）；If catalyst is acid, then alkali cleaning is used, removes acidic catalyst, washing.Then have
Machine is mutually through drier（Anhydrous magnesium sulfate, anhydrous sodium sulfate, dead plaster etc.）Dry, revolving removes solvent to get to organic
Silicon polymer.
In the present invention, the organosilicon polymer can be used for film preparation, it can also be used to composite material, photoresist, light
Waveguide material, adhesive etc..This polymer can cure at 200 ~ 350 DEG C, obtain heat safe transparent optical material.
In the present invention, the organosilicon polymer can be carried out using two-fold nitrogen class organic compound as photosensitive crosslinker
Photoetching.Specifically polymer and the configuration of two-fold nitrogen class organic compound are then spin coated onto in organic solvent（500~5000
Rev/min）Film forming, then carry out front baking.Under ultraviolet light using cover plate carry out photoetching.The region of illumination crosslinks, and not
The place of illumination does not crosslink then, is soluble in developer.Heating, heat cure can be obtained after being carried out again after development
Cured patterned graph.
Wherein solvent can be toluene, dimethylbenzene, mesitylene, dichloromethane, chloroform, n-hexane, petroleum ether, ring
Hexane, normal heptane, normal octane, methanol, ethyl alcohol, isopropanol, n-butanol, acetone, methyl ethyl ketone, cyclobutanone etc..
The two-fold nitrogen class organic compound can be following one or more of works as：
。
The front baking is heated on baking oven or thermal station, and temperature can be room temperature to 150 DEG C, time 2--100 point
Clock.
The developer be petroleum ether, ethyl acetate, propyl acetate, butyl acetate, n-hexane, hexamethylene, normal heptane,
The mixed liquor of one or more of cyclohexanone, acetone, methyl ethyl ketone, ethyl alcohol, methanol, isopropanol, water etc. configuration.
The heating, heat cure are that first heating removes solvent in thermal station, then is placed into baking oven or tube furnace, are heated up
Solidification can be arranged from 150 DEG C of -300 DEG C of temperature programmings, realize that polymer is fully cured.
By taking PVS-BCB polymer and its photoetching as an example.
First with methyl ethylene disiloxane and 4- bromines BCB under palladium catalytic action, prepare this with double
The organosilicon BCB monomers of silicone functionalities.Precipitation is filtered out after reaction, is further washed by hexamethylene, and revolving is dense
Contracting, vacuum distillation obtain monomer.It confirmed its structure using the methods of infrared, nuclear-magnetism characterization.
Utilize this monomer M1, end-capping reagent is added, is hydrolyzed under alkaline condition, polycondensation reaction prepares linearly low
Polymers PVS-BCB.
This low polymer can be by spin-coating film, then in temperature programming（180~300℃）It is cured later；Also may be used
Bulk is prepared to cure in a mold.The glass transition temperature of this material is higher than 350 DEG C, linear expansion coefficient 32.8ppm/
DEG C, thermal weight loss temperature in nitrogen atmosphere（10 DEG C/minute of heating rate）At 490 DEG C or more.
By two-fold nitrogen organic compound BAC-M and PVS-BCB configuration in mesitylene, photoetching figure is prepared for by photoetching
Case.Experiment shows that PVS-BCB has good lithography performance.
It is this have excellent performance, the oligomer with lithography performance has in Electronic Packaging, photoelectric device, integrated circuit fields
Broad prospect of application.It can directly be applied, can also be modified by the way that other organic and inorganic modifying agent are added.As made
For encapsulating material, it is applied to electronic devices or the photoelectric devices such as solar cell, display device, LED, MEMS.It also is used as
Optical device or optical film materials, be alternatively arranged as semiconductor, integrated circuit fields low dielectric layer between dielectric material, low
Dielectric lithography glue etc..It can be also used for the preparation of high-property resin composite material.
Description of the drawings
Fig. 1 is the dynamic mechanical analysis curve of sample after PVS-BCB solidifications.
Fig. 2 is the thermo-mechanical analysis curve of sample after PVS-BCB solidifications.
Fig. 3 is the lithographic images that BAC-M and PVS-BCB configures photoresist.
Specific implementation mode
Embodiment 1, the preparation of the M of monomer containing benzocyclobutene
In there-necked flask, it is separately added into 4- bromines benzocyclobutene 9.54g, methylvinyldimethoxysilane 6.79g, triethylamine
9ml, acid chloride 0.169g, three（O-tolyl）Phosphine 0.447g, acetonitrile 60ml, the lower 90 DEG C of heating reflux reactions of nitrogen protection are for 24 hours.
After reaction, revolving removes solvent, after petroleum ether and stirring is added, filtering.Filtrate revolving remove petroleum ether, remaining concentrate into
Row vacuum distillation obtains monomer M（Yield 68%）.
Embodiment 2, acid catalyzed hydrolysis prepare M and diphenyl diethoxy silane cocondensation poly polymer I
By monomer M 4.68g, diphenyl diethoxy silane 1.36g, acetic acid 0.2g, water 0.561g, trimethylethoxysilane
0.483g is added in three-necked bottle.90 DEG C of heating are reacted 5 hours.20 milliliters of toluene are added after reaction, respectively with saturation
Sodium bicarbonate aqueous solution is washed three times, and deionization washing is primary.Anhydrous sodium sulfate is dried, filtering.Revolving removes solvent, obtains sticky
Light yellow liquid.
Embodiment 3, alkali catalyzed hydrolysis method prepare M and diphenyl diethoxy silane cocondensation poly polymer II
By monomer M 4.68g, diphenyl diethoxy silane 1.36g, 25% aqueous solution 0.161g of tetramethylammonium hydroxide, water
0.561g, trimethylethoxysilane 0.483g are added in three-necked bottle.90 DEG C are heated 4.5 hours, and methanol and ethyl alcohol are steamed.Instead
20 milliliters of toluene are added after answering, are washed three times with dilute hydrochloric acid respectively, the NaCl aqueous solutions of saturation are washed 1 time, deionization washing one
It is secondary.Anhydrous sodium sulfate is dried, filtering.Revolving obtains sticky light yellow liquid.
Embodiment 4, alkali catalyzed hydrolysis method prepare M and diphenyl diethoxy silane cocondensation poly polymer II
By monomer M 4.68g, diphenyl diethoxy silane 1.36g, 25% aqueous solution 0.161g of tetramethylammonium hydroxide, water
0.561g, trimethylethoxysilane 0.483g are added in three-necked bottle.90 DEG C are heated 4.5 hours, and methanol and ethyl alcohol are steamed.So
N-hexane azeotropic band water is added afterwards, continues to be warming up to 120 DEG C steaming solvent, then be warming up to 150 DEG C of decomposition catalyst tetramethyl hydrogen
Amine-oxides, oil pump degassing, finally obtain sticky light yellow liquid.
Embodiment 5, alkali hydrolysis method prepare polymer P VS-BCB
By monomer M 4.68g, tetramethylammonium hydroxide 25% aqueous solution 0.186g, trimethylethoxysilane 0.483g are added to
In three-necked bottle.90 DEG C are heated 4.5 hours, and methanol and ethyl alcohol that reaction generates are steamed.Then n-hexane azeotropic band water is added, continues
It is warming up to 120 DEG C and steams solvent, then be warming up to 150 DEG C of decomposition catalyst tetramethylammonium hydroxide, vacuum oil pump degassing, finally
To sticky light yellow liquid.
Embodiment 6, alkali hydrolysis method prepare polymer P VS-BCB
By monomer M 2.079g, tetramethylammonium hydroxide 25% aqueous solution 0.161g, water 0.582g, trimethylethoxysilane
0.483g is added in three-necked bottle.90 DEG C are heated 4.5 hours, and methanol and ethyl alcohol are steamed.Toluene is added after reaction, uses respectively
Dilute hydrochloric acid is washed three times, and the NaCl aqueous solutions of saturation are washed 1 time, and deionization washing is primary.Anhydrous sodium sulfate is dried, filtering.It rotates
To sticky light yellow liquid.
Embodiment 7, PVS-BCB bulk polymerizations
PVS-BCB oligomer prepared by embodiment 6 is added in glass mold, heating is passed through（200 DEG C, 1h；230 DEG C,
1h；260 DEG C, 1h；300 DEG C, 0.5h）Solidification, obtains light yellow clear bulk.It is levied using DMA table（Figure of description 1）It was found that material
The glass transition temperature of material is higher than 400 DEG C, is characterized using TMA and finds that the coefficient of thermal expansion of material is 32ppm/ DEG C（See explanation
Attached drawing 2）;It is characterized using thermal weight loss and finds that 5% thermal weight loss temperature of material is 500 DEG C.
Embodiment 8, the configuration and photoetching of photoresist
By oligomer PVS-BCB0.254g, mesitylene 0.792g and double azido compound（BAC-M）0.017g is configured in aluminium
In the bottle of foil cladding, it is stirred overnight.Photoetching process operation is carried out between photoetching within second day.Progress spin coating spin coating first, then
Front baking 10min is carried out in thermal station for 90 DEG C.Then it is exposed using ultraviolet lamp, is developed later using developer solution, then carried out
After cure, obtain photoengraving pattern, see Figure of description 3.
Claims (18)
1. a kind of functionalized organosilicon polymer of benzocyclobutene, structural formula are as follows：
Wherein, R1, R2, R3It is respectively selected from methyl, ethyl, propyl, allyl, isopropyl, cyclohexyl, phenyl, hydrogen atom, carbon carbon
Double bond, hydroxypropyl, chloropropyl, aminopropyl；M, n round numbers；Wherein m is more than 2；N is more than or equal to 0.
2. a kind of preparation method of the functionalized organosilicon polymer of benzocyclobutene as described in claim 1, feature exist
In by one or more kinds of siloxanyl monomers, under acid or base catalyst effect, by hydrolysis-condensation reaction, being prepared
The functionalized organosilicon polymer of benzocyclobutene；The siloxanyl monomers at least one is containing the functionalized organosilicons of BCB
The structural formula of M, organosilicon M are as follows：
R4 is methoxyl group, ethyoxyl or isopropoxy.
3. preparation method according to claim 2, which is characterized in that the organosilicon M structure formula is one kind as follows：
。
4. preparation method according to claim 2 or 3, which is characterized in that the siloxanyl monomers, in addition to organosilicon M,
Further include one or more in other following organic silicon monomers：Dimethoxydiphenylsilane, diphenyl diethoxy silane,
Dimethyl diethoxysilane, diethyldiethoxysilane, aminomethyl phenyl diethoxy silane, chloromethyl methyl dimethoxy oxygroup
Silane.
5. preparation method according to claim 4, which is characterized in that other described organic silicon monomers further include sealing end
Agent, the end-capping reagent are selected from trimethylethoxysilane, trimethylmethoxysilane, diphenylmethylethoxysilane, triphen
Base oxethyl silane, triphenylmethoxy silane, Vinyldimethylethoxysilane, dimethylvinylmethoxysiiane,
Dimethylethoxysilane, dimethyl methoxy silane, hexamethyldisiloxane, tetramethyl divinyl disiloxane, 1,3-
Four ethylene disiloxane of dimethyl -1,1,3,3-, 1,1,3,3- tetramethyl -1,3- diphenyl disiloxane, 1,3- divinyl -
1,3- dimethyl -1,3- diphenyl disiloxane, tetramethyl disiloxane, decamethyl tetrasiloxane.
6. preparation method according to claim 2, which is characterized in that in the catalyst, alkali is tetramethyl hydroxide
Ammonium or alkali glue；Acid is sulfuric acid, formic acid, acetic acid or methanesulfonic acid.
7. preparation method according to claim 2, which is characterized in that in the hydrolysis-condensation reaction, using following molten
One or more of agent：Alkane solvent, tetrahydrofuran, water, toluene, benzene, dimethylbenzene, dioxane, 2- methyl tetrahydrochysene furans
It mutters, dichloromethane, 2,5- dimethyl-tetrahydrofurans, glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether.
8. preparation method according to claim 2, which is characterized in that in the hydrolysis-condensation reaction, first use simple
Reflux, after use instead reflux band water installations, so that hydrolysis-condensation reaction is fully carried out；Or simple reflux is first used, after
Use normal pressure or vacuum distillation apparatus instead, react fully progress；Either directly using reflux band water installations or distilling apparatus.
9. preparation method according to claim 2, which is characterized in that the hydrolysis-condensation reaction, reaction temperature model
It encloses for room temperature to 120 DEG C, the reaction time is 1 ~ 24 hour.
10. preparation method according to claim 6, which is characterized in that after the hydrolysis-condensation reaction, be such as catalyzed
Agent is tetramethylammonium hydroxide, decomposes by being warming up to 130~160 DEG C and removes catalyst；Or petroleum ether, dichloromethane is added
Alkane, ethyl acetate or butyl acetate further carry out pickling, remove basic catalyst；If catalyst is acid, then alkali cleaning is used, is removed
Remove acidic catalyst；Then it washes；Finally with organic phase through desiccant dryness, revolving removes solvent, obtains organosilicon polymer.
11. the functionalized organosilicon polymer of benzocyclobutene as described in claim 1, is preparing film, composite material, light
Application in photoresist, optical waveguide material, adhesive.
12. application according to claim 11, which is characterized in that the application as photoresist is to gather organosilicon
It closes object and carries out photoetching as photosensitive crosslinker using two-fold nitrogen class organic compound, the specific steps are：By organosilicon polymer and
The configuration of two-fold nitrogen class organic compound is in organic solvent, so with 500 ~ 5000 revs/min of rotating speed spin-coating films, then before carrying out
It dries；Under ultraviolet light using cover plate carry out photoetching；The region of illumination crosslinks, and the place of non-illumination does not occur then
Crosslinking, is soluble in developer；Heating, heat cure are to get to cured patterned graph after being carried out again after development.
13. application according to claim 12, which is characterized in that the organic solvent is selected from toluene, dimethylbenzene, equal three
Toluene, dichloromethane, chloroform, n-hexane, petroleum ether, hexamethylene, normal heptane, normal octane, methanol, ethyl alcohol, isopropanol, just
Butanol, acetone, methyl ethyl ketone, cyclobutanone.
14. application according to claim 12, which is characterized in that the two-fold nitrogen class organic compound is with lower structure
One or more of formula compound：
。
15. application according to claim 12, which is characterized in that the front baking is heated on baking oven or thermal station,
Temperature is room temperature to 150 DEG C, time 2--100 minute.
16. application according to claim 12, which is characterized in that the developer is petroleum ether, ethyl acetate, acetic acid
Propyl ester, butyl acetate, n-hexane, hexamethylene, normal heptane, cyclohexanone, acetone, methyl ethyl ketone, ethyl alcohol, methanol, isopropanol, water
In one kind or many of configuration mixed liquor.
17. application according to claim 12, which is characterized in that the heating, heat cure are first to be heated in thermal station
Solvent is removed, then is placed into baking oven or tube furnace, elevated cure, setting realizes polymer from 150 DEG C of -300 DEG C of temperature programmings
It is fully cured.
18. application according to claim 12, which is characterized in that the functionalized polymerizable organosilicon of the benzocyclobutene
Object is PVS-BCB polymer, which is prepared by following process：
First by methyl ethylene disiloxane and, 4- bromines BCB is prepared under palladium catalytic action with double siloxanes
The organosilicon BCB monomers of functional group；Then this monomer M is utilized1, end-capping reagent is added, is hydrolyzed, contracts under alkaline condition
Poly- reaction, is prepared linear oligomer, is denoted as PVS-BCB polymer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479087A (en) * | 2022-03-14 | 2022-05-13 | 中国科学院化学研究所 | Benzocyclobutene functionalized polysiloxane and preparation method thereof |
| TWI808442B (en) * | 2020-07-02 | 2023-07-11 | 美商羅門哈斯電子材料有限公司 | Bisbenzocyclobutene formulations |
| CN117111405A (en) * | 2023-08-04 | 2023-11-24 | 西南科技大学 | Preparation of linear polysiloxane low dielectric loss photosensitive resin and application of photoetching patterning |
| CN117826532A (en) * | 2024-03-05 | 2024-04-05 | 烟台舜康生物科技有限公司 | Preparation method of photoresist without light initiator |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405655A (en) * | 2006-03-16 | 2009-04-08 | 旭硝子株式会社 | Negative-type photosensitive fluorinated aromatic resin composition |
| US20120070781A1 (en) * | 2009-03-31 | 2012-03-22 | Dai Nippon Printing Co., Ltd. | Base generator, photosensitive resin composition, pattern forming material comprising the photosensitive resin composition, pattern forming method using the photosensitive resin composition and products comprising the same |
| CN102520584A (en) * | 2011-09-13 | 2012-06-27 | 复旦大学 | Photosensitive benzocyclobutene resin compound and preparation method thereof as well as patterning method thereof |
| CN103665025A (en) * | 2013-12-31 | 2014-03-26 | 复旦大学 | Adamantyl benzocyclobutene monomer and synthesizing method of polymer of adamantyl benzocyclobutene monomer |
| JP2014101425A (en) * | 2012-11-19 | 2014-06-05 | Canon Inc | Cage silsesquioxane, crosslinked cage silsesquioxane, and optical element having the same |
| CN105778096A (en) * | 2014-12-19 | 2016-07-20 | 中国科学院上海有机化学研究所 | Manufacturing method and application of benzocyclobutenyl containing silicon resin |
| CN106866722A (en) * | 2017-01-12 | 2017-06-20 | 复旦大学 | A kind of organo-silicon compound containing benzocyclobutene functionalization and preparation method thereof |
| CN106893032A (en) * | 2015-12-21 | 2017-06-27 | 罗门哈斯电子材料有限责任公司 | Arylcyclobutene |
-
2018
- 2018-04-23 CN CN201810364065.2A patent/CN108586748B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405655A (en) * | 2006-03-16 | 2009-04-08 | 旭硝子株式会社 | Negative-type photosensitive fluorinated aromatic resin composition |
| US20120070781A1 (en) * | 2009-03-31 | 2012-03-22 | Dai Nippon Printing Co., Ltd. | Base generator, photosensitive resin composition, pattern forming material comprising the photosensitive resin composition, pattern forming method using the photosensitive resin composition and products comprising the same |
| CN102520584A (en) * | 2011-09-13 | 2012-06-27 | 复旦大学 | Photosensitive benzocyclobutene resin compound and preparation method thereof as well as patterning method thereof |
| JP2014101425A (en) * | 2012-11-19 | 2014-06-05 | Canon Inc | Cage silsesquioxane, crosslinked cage silsesquioxane, and optical element having the same |
| CN103665025A (en) * | 2013-12-31 | 2014-03-26 | 复旦大学 | Adamantyl benzocyclobutene monomer and synthesizing method of polymer of adamantyl benzocyclobutene monomer |
| CN105778096A (en) * | 2014-12-19 | 2016-07-20 | 中国科学院上海有机化学研究所 | Manufacturing method and application of benzocyclobutenyl containing silicon resin |
| CN106893032A (en) * | 2015-12-21 | 2017-06-27 | 罗门哈斯电子材料有限责任公司 | Arylcyclobutene |
| CN106866722A (en) * | 2017-01-12 | 2017-06-20 | 复旦大学 | A kind of organo-silicon compound containing benzocyclobutene functionalization and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| TAIYO SHIMIZU等: "Transparent Ethenylene-Bridged Polymethylsiloxane Aerogels:", 《LANGMUIR》 * |
| 晨光化工研究院有机硅编写组: "《有机硅单体及聚合物》", 31 December 1986, 化学工业出版社 * |
| 袁源等: "新型苯并环丁烯官能化ＰＯＳＳ及其衍生聚合物的", 《化工新型材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI808442B (en) * | 2020-07-02 | 2023-07-11 | 美商羅門哈斯電子材料有限公司 | Bisbenzocyclobutene formulations |
| CN114479087A (en) * | 2022-03-14 | 2022-05-13 | 中国科学院化学研究所 | Benzocyclobutene functionalized polysiloxane and preparation method thereof |
| CN114479087B (en) * | 2022-03-14 | 2023-01-20 | 中国科学院化学研究所 | Benzocyclobutene functionalized polysiloxane and preparation method thereof |
| CN117111405A (en) * | 2023-08-04 | 2023-11-24 | 西南科技大学 | Preparation of linear polysiloxane low dielectric loss photosensitive resin and application of photoetching patterning |
| CN117826532A (en) * | 2024-03-05 | 2024-04-05 | 烟台舜康生物科技有限公司 | Preparation method of photoresist without light initiator |
| CN117826532B (en) * | 2024-03-05 | 2024-05-07 | 烟台舜康生物科技有限公司 | Preparation method of photoresist without light initiator |
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