CN100384799C - Fluorinated compound, fluoropolymer and process for its production - Google Patents

Fluorinated compound, fluoropolymer and process for its production Download PDF

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CN100384799C
CN100384799C CNB2004800315383A CN200480031538A CN100384799C CN 100384799 C CN100384799 C CN 100384799C CN B2004800315383 A CNB2004800315383 A CN B2004800315383A CN 200480031538 A CN200480031538 A CN 200480031538A CN 100384799 C CN100384799 C CN 100384799C
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fluoropolymer
fluorine
polymkeric substance
polymerization
solvent
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CN1871196A (en
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武部洋子
横小路修
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AGC Inc
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Asahi Glass Co Ltd
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Abstract

A fluorine compound which has functional groups in a high concentration, can hence have sufficient properties attributable to the functional groups, and is highly transparent in a wide wavelength region. It is a fluorinated diene represented by the following formula (1): CF2=CFCH2CH(C(R<1>)(R<2>)(OH))CH2CH=CH2 (1) wherein R<1> and R<2> each independently represents fluorine or C5 or lower fluoroalkyl.

Description

Fluorochemicals, fluoropolymer and manufacture method thereof
Technical field
The present invention relates to new fluorochemicals, fluoropolymer and manufacture method thereof.
Background technology
As fluoropolymer with functional group, it is known that to have at fluorine be the fluoropolymer that contains functional group that uses in ion-exchange membrane or the solidified nature fluorine resin coating etc., but they all are basic frameworks is straight catenate polymkeric substance, by being that the fluoroolefin of representative and the monomeric copolymerization with functional group get with the tetrafluoroethylene.
In addition, also known have a functional group of containing, and the polymkeric substance that has fluorine-containing aliphatics ring structure in main chain is as the method that imports functional group in the polymkeric substance that has fluorine-containing aliphatics ring structure in the chain linked to owner, the known method that utilization is arranged through the terminal group of polymerization resulting polymers; The pyroprocessing polymkeric substance makes the side chain of polymkeric substance or the method that terminal oxygenolysis forms functional group; Make monomer copolymerizable, as required by being added the method (for example, referring to Patent Document 1,2,3,4) that processing such as water decomposition import with functional group.
As the method that imports functional group in the polymkeric substance that has fluorine-containing aliphatics ring structure in the chain linked to owner, though aforesaid method is arranged, yet import in the method for functional group by the terminal group of handling polymkeric substance, have the shortcoming that the functional group concentration is low, can not obtain sufficient characteristics of functional groups.Make in addition in the introduction method of monomer copolymerizable, exist, then degradation problem under the mechanical characteristics that causes by vitrification point (Tg) decline as functional group concentration's height with functional group.
[patent documentation 1] Japanese patent laid-open 4-189880 communique
[patent documentation 2] Japanese patent laid-open 4-226177 communique
[patent documentation 3] Japanese patent laid-open 6-220232 communique
[patent documentation 4] international brochure that discloses No. 02/064648
The announcement of invention
The problem that invention will solve
The problem that the present invention will solve provides functional group concentration's height, can obtain the characteristic of sufficient functional group, has fluorochemicals, fluoropolymer and the manufacture method thereof of high transparent in the big wavelength region of scope.Provide in addition, as the chemical amplification type anti-corrosion agent, particularly can form far ultraviolet rays yue or F such as KrF, ArF excimer lasers 2The ultraviolet transparency of excimer laser equal vacuum, dry corrosion is good and the corrosion-resistant composition of the corrosion-resisting pattern that sensitivity, resolving power dissolution rate, flatness etc. are all good.In addition, also being provided at liquid soaks in photoetching (lithography) operation protection etchant resist and is not subjected to liquid to soak the etchant resist protective membrane of solvent effect.
Solve the method for problem
The present invention is for solving the following invention of above-mentioned problem.
The invention provides the fluorine-containing diene shown in the following formula (1).
CF 2=CFCH 2CH (C (R 1) (R 2) (OH)) CH 2CH=CH 2(1) in the formula, R 1With R 2Represent independently that respectively fluorine atom or carbonatoms are smaller or equal to 5 fluoroalkyl.
The invention provides the fluorine-containing diene shown in (1) that has following formula fluoropolymer (A) and manufacture method thereof through cyclopolymerization gained monomeric unit.
In addition, the present invention also provides etchant resist protective membrane composition, it is characterized in that, contains the solvent of fluoropolymer (A), dissolving or dispersion fluoropolymer (A).
Effect of the present invention
By the present invention, can be manufactured on the fluoropolymer that main chain has the aliphatics ring structure, has hydroxyl at side chain.The fluoropolymer of gained of the present invention has high chemical stability and thermotolerance.And, can give full play to the hydroxyl characteristic owing in side chain, imported hydroxyl, and can not cause that Tg descends, this is difficult to reach to fluoropolymer in the past.Particularly, owing to have the high hydroxyl of acidity at the ring side chain, therefore the solvability to alkaline aqueous solution improves.And has high transparent in the wide range of wavelengths scope.
The best mode that carries out an invention
By the present invention, can provide following general formula (1) expression fluorine-containing diene (below, be called fluorine-containing diene (1)), have the fluoropolymer (A) and the manufacture method thereof of fluorine-containing diene (1) cyclopolymerization gained monomeric unit.
CF 2=CFCH 2CH (C (R 1) (R 2) (OH)) CH 2CH=CH 2(1) in the formula (1), R 1With R 2Represent independently that respectively fluorine atom or carbonatoms are smaller or equal to 5 fluoroalkyl.Particularly, R 1And/or R 2Being preferably trifluoromethyl, preferably is trifluoromethyl simultaneously.
Fluorine-containing diene of the present invention can be synthetic by known method.For example, with CH 2=CHC (R 1) (R 2) OH is as initial substance, in the presence of radical initiator, makes CF 2The ClCFClI addition forms CF on two keys 2ClCFClCH 2CHIC (R 1) (R 2) after the OH, make it and CH 2=CHCH 2The MgCl reaction forms CF 2ClCFClCH 2CH (C (R 1) (R 2) OH) CH 2CH=CH 2Afterwards, carry out dechlorination again and get.By changing R 1, R 2, can obtain various fluorine-containing diene described as follows (1).
As the concrete example of fluorine-containing diene of the present invention (1), can exemplify as followsly, but be not limited to this.
Fluorine-containing diene (1) cyclopolymerization under comparatively gentle condition obtains encircling the cyclized polymer that side chain has hydroxyl.
By the cyclopolymerization of fluorine-containing diene (1), generate the monomeric unit of following (a)～(c).Think that by spectrographic analytical results etc. fluoropolymer (A) is the polymer with the structure that contains the monomeric unit more than a kind or a kind that is selected from monomeric unit (a), monomeric unit (b) and monomeric unit (c).
The monomeric unit (below, be designated as monomeric unit (1)) that fluoropolymer (A) better has fluorine-containing diene (a 1) cyclopolymerization gained in addition, the hydroxyl that also has a monomeric unit (1) is by the monomeric unit of end-blockingization (below, be designated as end-blocking monomeric unit (1)).The ratio of end-blocking monomeric unit (1) with respect to the total of monomeric unit (1) and end-blocking monomeric unit (1), is preferably smaller or equal to 50 moles of %, particularly preferably 15～40 moles of %.End-blockingization is exactly the hydrogen atom with closure group substituted hydroxy.By the concrete example of the hydroxyl of end-blockingization, can exemplify as-OCH 3,-OCF 3,-O (t-C 4H 9) ,-OCH 2OCH 3,-OCH 2OC 2H 5,-OCH 2OCH 2OCH 3,-OCH 2OCH 2CF 3,-OCOO (t-C 4H 9) ,-OCH (CH 3) OC 2H 5, 2-THP trtrahydropyranyl oxygen base and following shown in group.
Figure C20048003153800061
The fluoropolymer (A) that contains monomeric unit (1) and end-blocking monomeric unit (1) can obtain by making fluorine-containing diene of end-blockingization and fluorine-containing diene (1) copolymerization with the hydroxy-end cappedization gained of fluorine-containing diene (1).Also can obtain in addition by hydroxy-end cappedization of a part of the monomeric unit (1) in the fluoropolymer (A) that will have monomeric unit (1).
In the fluoropolymer (A) except monomeric unit (1), in the scope of not destroying its characteristic, can also be in addition from the monomeric unit of other free radical polymerization monomer (but, except that end-blocking monomeric unit (1)).Should be preferably smaller or equal to 50 moles of %, particularly preferably smaller or equal to 15 moles of % from the monomeric unit of other free radical polymerization monomer ratio with respect to whole monomeric units.
But, can exemplify as alpha-olefines such as ethene, propylene, iso-butylenes as other free radical polymerization monomer of example; Fluorine containing olefine such as tetrafluoroethylene, R 1216 class; Fluorine-containing cyclic monomer classes such as perfluor (2,2-dimethyl-1,3-Er Evil is luxuriant); Perfluor (butenyl vinyl ether) but etc. the dienes of cyclopolymerization; 1,1,2,3,3-five fluoro-4-trifluoromethyl-4-hydroxies-1,6-heptadiene, 1,1,2-three fluoro-4-[3,3,3-three fluoro-2-hydroxyls-2-trifluoromethyl propyl group]-1, but the hydrofluorination dienes of cyclopolymerizations such as 6-heptadiene; Esters of acrylic acid such as methyl acrylate, Jia Jibingxisuanyizhi; Vinyl esters such as vinyl acetate, M-nitro benzoic acid vinyl acetate, golden steel alkanoic acid vinyl acetate; Vinyl ethers such as ethyl vinyl ether, cyclohexyl vinyl ether; Cyclic olefins such as tetrahydrobenzene, norbornylene, norbornadiene; Maleic anhydride, ethylene chloride etc.
Fluoropolymer of the present invention (A) can by make fluorine-containing diene (1) under the polymerization initiating accident sequence separately polymerization or and other copolymerizable monomer copolymerizable get.As the polymerization initiating accident sequence, so long as Raolical polymerizable is carried out smoothly, then there is not any qualification, for example free-radical generating agent, light, ionizing radiation etc.Free-radical generating agent particularly preferably, as free-radical generating agent, for example superoxide, azo-compound, persulphate etc.In free-radical generating agent, be preferably superoxide.As concrete superoxide, can exemplify following compound.
C 6H 5-C(O)O-OC(O)-C 6H 5
C 6F 5-C(O)O-OC(O)-C 6F 5
C 3F 7-C(O)O-OC(O)-C 3F 7
(CH 3) 3C-C(O)O-OC(O)-C(CH 3) 3
(CH 3) 2CH-C(O)O-OC(O)-CH(CH 3) 2
(CH 3) 3C-C 6H 10-C(O)O-OC(O)-C 6H 10-C(CH 3) 3
(CH 3) 3C-O-C(O)O-OC(O)-O-C(CH 3) 3
(CH 3) 2CH-O-C(O)O-OC(O)-O-CH(CH 3) 2
(CH 3) 3C-C 6H 10-O-C(O)O-OC(O)-O-C 6H 10-C(CH 3) 3
In the formula ,-C 6H 5The expression phenyl ,-C 6F 5Represent seven fluorophenyls ,-C 6H 10-expression cyclohexylidene.
The polymeric method does not have special qualification, can exemplify as the monomeric mass polymerization of direct polymerization; Solubilized or disperse fluorine-containing diene (1) and other monomeric fluorinated hydrocarbons, chlorinated hydrocarbon, fluorine chlorinated hydrocarbon, alcohol, hydrocarbon polymer, other organic solution in the solution polymerization carried out; In the water-based medium, there is or do not exist the suspension polymerization of carrying out under the suitable organic solvent; The letex polymerization of adding emulsifying agent in hydrotropisms's medium and carrying out etc.
Carrying out polymeric temperature and pressure does not have special qualification yet, better considers monomeric boiling point, heating source, removes various factors such as heat of polymerization, comes selected suitable condition.For example, suitable temperature can be between 0 ℃～200 ℃, selected, about in room temperature～100 ℃, practical optimal temperature can be set.In addition, can be under reduced pressure also can depress adding as polymerization pressure, practical can be about normal pressure～100 normal atmosphere, even implement suitable polymerization about normal pressure～10 normal atmosphere.
The molecular weight of fluoropolymer of the present invention (A) as long as can be dissolved in equably in the aftermentioned organic solvent (C), can be coated on the base material equably; just have no particular limits, the number-average molecular weight that is scaled polystyrene usually be 1,000～100,000 o'clock comparatively suitable; more preferably 2,000～30,000.By making number-average molecular weight the possibility occurrence as the corrosion-resisting pattern of gained takes place that residual film ratio bad, after developing descends, degradation is not measured situation under shape stability during pattern thermal treatment be reduced more than or equal to 1,000.In addition, make number-average molecular weight, can keep the coating of aftermentioned corrosion-resistant composition well, can keep good development smaller or equal to 100,000.
Fluoropolymer of the present invention (A) can be used as photo-resist and uses with base polymer.That is, (C) composition that contains fluoropolymer (A), is subjected to the acidic acid-producing cpd of rayed (B) and contains organic solvent by formation can be used as corrosion-resistant composition and uses.Below, better form with fluoropolymer (A), the fluoropolymer (A) that promptly has monomeric unit (1) and an end-blocking monomeric unit (1) is example, describes fluoropolymer (A) in detail as the corrosion-resistant composition of base polymer (below, be designated as corrosion-resistant composition (D)).
Above-mentioned, be subjected to the acidic acid-producing cpd of rayed (B) and generate acid by exposure.Be subjected to the effect of this acid, make part or all end-blocking base division (going end-blockingization) of the end-blocking monomeric unit (1) in the fluoropolymer (A).As a result, exposure portion is soluble in alkaline-based developer, can form the corrosion-resisting pattern of eurymeric by alkaline-based developer.As this acidic acid-producing cpd of rayed (B) that is subjected to, can adopt the acid-producing cpd that in common chemical amplification type anti-corrosion agent, uses, can exemplify as salt, halide-containing, diazo-ketones compound, sulphones, sulfoacid compound etc.As the example of these acid-producing cpds (B), can exemplify following example.
As salt, can exemplify salt compounded of iodine, sulfonium salt, microcosmic salt, diazonium salt, pyridinium salt etc.As the concrete example of salt preferably, can exemplify as phenylbenzene iodine fluoroform sulphonate, phenylbenzene iodine pyrene sulfonate, phenylbenzene iodine dodecylbenzene sulfonate, two (4-tert-butyl-phenyl) iodine fluoroform sulphonate, two (4-tert-butyl-phenyl) iodine dodecylbenzene sulfonate, the triphenylsulfonium fluoroform sulphonate, triphenylsulfonium king's hydrochlorate, the triphenylsulfonium perfluoro octane sulfonate, the triphenylsulfonium hexafluoro antimonate, 1-(naphthyl acetylmethyl) sulphur fluoroform sulphonate, cyclohexyl methyl (2-oxo cyclohexyl) sulfonium fluoroform sulphonate, dicyclohexyl (2-oxo cyclohexyl) sulfonium fluoroform sulphonate, dimethyl (4-hydroxyl naphthyl) sulfonium tosylate, dimethyl (4-hydroxyl naphthyl) sulfonium dodecylbenzene sulfonate, dimethyl (4-hydroxyl naphthyl) sulfonium naphthalenesulfonate, the triphenylsulfonium camsilate, (4-hydroxy phenyl) benzyl methyl sulfonium tosylate etc.
As halide-containing, can exemplify as the hydrocarbon polymer that contains alkylhalide group, the heterogeneous ring compound that contains alkylhalide group etc.As concrete example, can exemplify as phenyl-two (trichloromethyl)-s-triazine, p-methoxy-phenyl-two (trichloromethyl)-s-triazine, naphthyl-two (trichloromethyl)-(trichloromethyl)-s-pyrrolotriazine derivatives such as s-triazine; 1,1-two (4-chloro-phenyl-)-2,2,2-trichloroethane etc.
As sulphones, for example, the α-diazonium compound of β-ketone sulfone, β-sulphonyl sulfone and these compounds etc.As concrete example, can exemplify as, 4-tri-benzoyl methyl sulfone,
Figure C20048003153800081
Base phenacyl sulfone, two (benzenesulfonyl) methane etc.As sulfoacid compound, can exemplify as alkyl sulfonic ester, alkyl sulfonyl imines, haloalkyl sulphonate, aromatic yl sulphonate, imino-sulphonate etc.As concrete example, can exemplify as bitter almond oil camphor tosylate, 1 8-naphthalene dicarboxylic acids imide fluoroform sulphonate etc.Acid-producing cpd (B) can use separately also can mix more than 2 kinds or 2 kinds and use.
Above-mentioned organic solvent (C) is not if the solvent of solubilized fluoropolymer (A) and these two kinds of compositions of acid-producing cpd (B) then has special qualification.Can exemplify as alcohols such as methyl alcohol, ethanol; Ketones such as acetone, mibk, pimelinketone; Acetates such as vinyl acetic monomer, N-BUTYL ACETATE; Aromatic hydrocarbon such as toluene, dimethylbenzene; Glycol monoalkyl such as propylene glycol monomethyl ether, dihydroxypropane single-ether ethers; Glycol monoalkyl ether-ether classes such as propylene glycol monomethyl ether acetate, Trivalin SF acetic ester etc.
Usually with respect to 100 mass parts of fluoropolymer (A), each components in proportions is suitably in the corrosion-resistant composition (D), acid-producing cpd (B) 0.1～20 mass parts and organic solvent (C) 50～2000 mass parts.More preferably, with respect to the fluoropolymer (A) of 100 mass parts, acid-producing cpd (B) is that 0.1～10 mass parts and organic solvent (C) are 100～1000 mass parts.
Usage quantity by making acid-producing cpd (B) can obtain sufficient sensitivity and development more than or equal to 0.1 mass parts, by making it smaller or equal to 10 mass parts, can fully guarantee the transparency to radioactive rays in addition, can obtain more accurate corrosion-resisting pattern.
Also with according to purpose, in corrosion-resistant composition (D), suitably mix the sour cracking behavior additive, the tensio-active agent that is used to improve coating that are used to improve the pattern contrast gradient, be used to adjust the nitrogenous basic cpd that produces sour pattern, be used to improve, be used to improve the conservatory preserving stabilizer of composition etc. with the fusible bonding agent of base material.In addition, corrosion-resistant composition of the present invention better is for mix after each composition the membrane filtration with 0.1～2 μ m at homogeneous.
By coating dry corrosion-resistant composition (D) on substrates such as silicon chip, can form etchant resist.Coating process can adopt spin coating, flow coat cloth, roller coat etc.On the etchant resist that forms, carry out rayed, carry out development treatment thereafter and form pattern by the mask that plots pattern.
As irradiates light, can exemplify the g line as wavelength 436nm, the ultraviolet rays such as i line of wavelength 365nm; The F of the KrF excimer laser of wavelength 248nm, the ArF excimer laser of wavelength 193nm, wavelength 157nm 2Far ultraviolet rays yue or vacuum ultraviolet rays such as excimer laser.Corrosion-resistant composition (D) is at the wavelength ultraviolet ray smaller or equal to 250nm, particularly wavelength ultraviolet ray (ArF excimer laser or the F smaller or equal to 200nm 2Excimer laser) as useful corrosion-resistant composition in the purposes of light source use.
As development treatment liquid, can adopt various alkaline aqueous solutions.As alkali, can exemplify as, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylphosphonihydroxide hydroxide amine, triethylamine etc.
Because fluoropolymer of the present invention (A) is water insoluble, and dissolves in developing solution, therefore can be used as the etchant resist protective membrane and use with base polymer.The solvent (E) and the fluoropolymer (A) of mixed dissolution or dispersion fluoropolymer (A) by be coated with drying on the etchant resist, form the etchant resist protective membrane.Coating process can adopt spin coating, flow coat, roller coat etc.On the etchant resist protective membrane that forms, carry out rayed, carry out development treatment thereafter, remove the pattern that the etchant resist protective membrane forms etchant resist by the mask that plots pattern.
Above-mentioned solvent (E) is not if the solvent of solubilized or dispersion fluoropolymer (A) then has special qualification.Be preferably soluble solvent.Also, therefore be preferably the solvent little to the influence of erosion resistant owing to will on etchant resist, be coated with.As solvent (E), can exemplify as alcohols such as methyl alcohol, ethanol; Ketones such as acetone, mibk, pimelinketone; Acetates such as vinyl acetic monomer, N-BUTYL ACETATE; Aromatic hydrocarbon such as toluene, dimethylbenzene; Glycol monoalkyl such as propylene glycol monomethyl ether, dihydroxypropane single-ether ethers; Glycol monoalkyl ether-ether classes such as propylene glycol monomethyl ether acetate, Trivalin SF acetic ester etc.; Fluorine series solvent class etc.Can be the mixture of above-mentioned solvent also, when being water-miscible organic solvent, also with the mixture of water.
With respect to the fluoropolymer (A) of 100 mass parts, usual solvents (E) is that 50～2000 mass parts are more suitable.Be preferably, with respect to the fluoropolymer (A) of 100 mass parts, solvent (E) is 100～1000 mass parts.Be preferably behind homogeneous mixing fluoropolymer (A) and solvent (E), the filter membrane with 0.1～2 μ m filters again.
Also can contain fluoropolymer (A) and solvent (E) other composition in addition.The liquid that described etchant resist protective membrane is used for improving resolving power more fortunately soaks photo-mask process to be used.Be preferably to soak in the photo-mask process and use at the liquid that makes water.
As irradiates light, can exemplify the g line as wavelength 436nm, the ultraviolet rays such as i line of wavelength 365nm; The F of the KrF excimer laser of wavelength 248nm, the ArF excimer laser of wavelength 193nm, wavelength 157nm 2Far ultraviolet rays yue or vacuum ultraviolet rays such as excimer laser.Fluoropolymer of the present invention (A) can be at the wavelength ultraviolet ray smaller or equal to 250nm, particularly wavelength ultraviolet ray (ArF excimer laser or the F smaller or equal to 200nm 2Excimer laser) in the purposes of using as light source useful etchant resist protective membrane with using in the base polymer.
Embodiment
Below, specify embodiments of the invention, but the present invention is not limited to this.
Abbreviation used in the following example is as follows.
THF: tetrahydrofuran (THF); BPO: benzoyl peroxide; PFBPO: peroxidation perfluor benzoyl; PFB: peroxidation perfluor butyryl; PSt; Polystyrene; R225: dichloro pentafluoropropane (solvent).
(embodiment 1)
[CF 2=CFCH 2CH (C (CF 3) 2OH) CH 2CH=CH 2Synthetic]
In the glass reactor of 1L (liter), add CF 2ClCFClI500g, CH 2=CHC (CF 3) 2OH 344g and BPO 32.6g were 95 ℃ of heating 71 hours.Thick liquid is reacted in underpressure distillation, obtains the CF of 544g 2ClCFClCH 2CHI (C (CF 3) 2OH) (55-58 ℃/0.2kPa).
In the glass reactor of 5L, add above-mentioned synthetic CF 2ClCFClCH 2CHI (C (CF 3) 2OH) 344g and dehydration THF1.7L are cooled to-70 ℃.To wherein in 4 hours, splashing into CH 2=CHCH 2The 2M-THF solution 1.8L of MgCl.
Be warming up to 0 ℃, stir after 16 hours, add saturated aqueous ammonium chloride 1.6L, be warming up to room temperature again.The separatory reaction solution concentrates organic layer with vaporizer, then carries out underpressure distillation, obtains the CF of 287g 2ClCFClCH 2CH (C (CF 3) 2OH) CH 2CH=CH 2(62-66 ℃/0.2kPa).Glass reactor to 1L adds zinc 97g and water 300g, is heated to 90 ℃.Splash into above-mentioned synthetic CF therein 2ClCFClCH 2CH (C (CF 3) 2OH) CH 2CH=CH 2287g stirred 24 hours.In reaction solution, splash into hydrochloric acid 70mL and stirred 2 hours, refilter separatory, carry out underpressure distillation, obtain the CF of 115g 2=CFCH 2CH (C (CF 3) 2OH) CH 2CH=CH 2(53-54 ℃/1kPa).
NMR spectrum
1H-NMR (399.8MHz, solvent: CDCl 3, benchmark: δ (ppm) tetramethylsilane): 2.53 (m, 5H), 3.49 (m, 1H), 5.15 (m, 2H), 5.79 (m, 2H).
19F-NMR (376.2MHz, solvent: CDCl 3, benchmark: CFCl 3) δ (ppm) :-73.6 (m, 6F) ,-104.1 (m, 1F) ,-123.1 (m, 1F) ,-175.4 (m, 1F).
(embodiment 2)
To internal volume is to add by embodiment 1 gained monomer 5g in the glass voltage-resistant reactor of 30mL.Then add 0.13gPFBPO as polymerization starter.Carry out freezing degassing tube sealing afterwards in the system, make its in the constant temperature vibrating trough (70 ℃) carry out polymerization 19 hours.After the polymerization,, splash into again in the hexane, make after the polymkeric substance redeposition, 115 ℃ of vacuum-dryings of implementing 18 hours with R225 diluting reaction solution.As a result, obtain having the amorphism polymkeric substance of fluorine-containing ring structure (below, be called polymer 1A) 3.32g on the main chain.Through with THF as the PSt conversion molecular weight that GPC measured of solvent being: number-average molecular weight (Mn) is 26300, weight-average molecular weight is (Mw) 56300, Mw/Mn=2.14.It is that the Tg that measures through differential scanning calorimeter (DSC) is 124 ℃, at room temperature is the polymkeric substance of white powder.Resulting polymkeric substance is dissolved in acetone, THF, vinyl acetic monomer, methyl alcohol, R225; Be insoluble to hexane.
Warp 19F-NMR and 1H-NMR be confirmed to be have following (d), (e) and (f) cyclized polymer of monomeric unit.
Figure C20048003153800111
(embodiment 3)
To internal volume is monomer 4g and the vinyl acetic monomer 2.2g that adds in the glass voltage-resistant reactor of 30mL by embodiment 1 gained.Then, interpolation is as the 3wt%R225 solution 6.23g of the PFB of polymerization starter.Carry out freezing degassing tube sealing afterwards in the system, make its in the constant temperature vibrating trough (20 ℃) carry out polymerization 41 hours.After the polymerization, reaction soln is splashed in the hexane, make after the polymkeric substance redeposition, 90 ℃ of vacuum-dryings of implementing 21 hours.As a result, obtain having the amorphism polymkeric substance of fluorine-containing ring structure (below, be called polymer 2A) 1.33g on the main chain.Through with THF as the PSt conversion molecular weight that GPC measured of solvent being: number-average molecular weight (Mn) is 15600, weight-average molecular weight is (Mw) 25100, Mw/Mn=1.61.It is to be 118 ℃, at room temperature to be the polymkeric substance of white powder through the Tg that differential scanning calorimeter (DSC) is measured.Resulting polymkeric substance is dissolved in acetone, THF, methyl alcohol; Be insoluble to R225.
(embodiment 4)
To internal volume is the monomer 10g that adds in the glass voltage-resistant reactor of 50mL by embodiment 1 gained.Then, interpolation is as the 3wt%R225 solution 40.6g of the PFB of polymerization starter.Carry out freezing degassing tube sealing afterwards in the system, make its in the constant temperature vibrating trough (20 ℃) carry out polymerization 18.5 hours.After the polymerization, reaction soln is splashed in the hexane with the R225 dilution again, make after the polymkeric substance redeposition, 120 ℃ of vacuum-dryings of implementing 15 hours.As a result, obtain having the amorphism polymkeric substance of fluorine-containing ring structure (below, be called polymer 3A) 8.5g on the main chain.Through with THF as the PSt conversion molecular weight that GPC measured of solvent being: number-average molecular weight (Mn) is 15500, weight-average molecular weight is (Mw) 26000, Mw/Mn=1.69.It is to be 117 ℃, at room temperature to be the polymkeric substance of white powder through the Tg that differential scanning calorimeter (DSC) is measured.Resulting polymkeric substance is dissolved in acetone, THF, methyl alcohol; Be insoluble to R225.
(embodiment 5)
To internal volume is monomer 2g and the diox 1.6g that adds in the glass voltage-resistant reactor of 30mL by embodiment 1 gained.Then, interpolation is as the 3wt%R225 solution 9.14g of the PFB of polymerization starter.Carry out freezing degassing tube sealing afterwards in the system, make its in the constant temperature vibrating trough (20 ℃) carry out polymerization 18 hours.After the polymerization, reaction soln is splashed in the hexane with the R225 dilution again, make after the polymkeric substance redeposition, 100 ℃ of vacuum-dryings of implementing 16 hours.As a result, obtain having the amorphism polymkeric substance of fluorine-containing ring structure (below, be called polymer 4A) 1.65g on the main chain.Through with THF as the PSt conversion molecular weight that GPC measured of solvent being: number-average molecular weight (Mn) is 8800, weight-average molecular weight is (Mw) 13400, Mw/Mn=1.53.It is to be 115 ℃, at room temperature to be the polymkeric substance of white powder through the Tg that differential scanning calorimeter (DSC) is measured.Resulting polymkeric substance is dissolved in acetone, THF, methyl alcohol; Dissolve in R225.
(embodiment 6)
In the glass reactor of 200ml, add, at room temperature stirred 20 hours by the polymkeric substance 4g of embodiment 4 gained, the 6.6wt% methanol solution 2.7g and the methyl alcohol 80g of sodium hydroxide.Behind the vaporizer concentration of reaction solution, be dissolved among the 120g of dehydration THF.Then add chloromethyl methyl ether 0.38g, at room temperature stirred 90 hours.Use the diatomite filtration reaction solution, concentrate with vaporizer.Dissolve enriched material in R225, separatory is carried out in washing again.In hexane, splash into the R225 layer, behind the redeposition polymkeric substance, 110 ℃ of vacuum-dryings of implementing 16 hours.As a result, obtain in main chain, having amorphism polymkeric substance (below, the be called polymer 5A) 3.3g of fluorine-containing ring structure.Warp 19F-NMR, 1H-NMR analyzes, and this polymeric methoxymethylation rate is 32 moles of %.Through using THF as the PSt conversion molecular weight that the GPC of solvent measures to be: number-average molecular weight (Mn) is 15800, weight-average molecular weight (Mw) is 25900, Mw/Mn=1.64.It is to be 111 ℃, at room temperature to be the polymkeric substance of white powder through the Tg that differential scanning calorimeter (DSC) is measured.The polymkeric substance of gained dissolves among acetone, THF, methyl alcohol and the R225.
The mensuration of the transparency of (embodiment 7～11) vacuum ultraviolet (VUV) scope 157nm
Make that each 1g of synthetic polymer 1A to 5A is dissolved among the propylene glycol monomethyl ether acetate 10g among the embodiment 2～6, with the PTFE system membrane filtration of aperture 0.2 μ m.At room temperature, use the rotary coating machine to change, the solution of the above-mentioned adjustment of coating on the CaF substrate with 1000.After the coating,, make the tunicle of thickness 0.15 μ m 100 ℃ of sintering 15 minutes.Measure the see through spectrum of these samples at 157nm.Transmittance (%) at 157nm is shown in table 1.In addition, the determinator of use is following device.
KV-201AD type extreme ultraviolet beam splitting system (spectrometer)
Wavelength region 120～300nm
Differentiating can 1～4nm
[table 1]
Polymer The transmittance of 157nm (%)
Embodiment 7 1A 90
Embodiment 8 2A 93
Embodiment 9 3A 93
Embodiment 10 4A 95
Embodiment 11 5A 90
(embodiment 12～13) are to the deliquescent mensuration of alkaline-based developer
Synthetic polymer 3A in embodiment 4 and 6, each 1g of 5A are dissolved among the propylene glycol monomethyl ether acetate 10g, use the PTFE system membrane filtration of aperture 0.2 μ m, be coated on the silicon substrate again.2.38% tetramethylammonium hydroxide aqueous solution that drips on the silicon substrate that is coated with polymkeric substance is estimated solvability.The results are shown in table 2.
[table 2]
Polymer Solvability to alkaline-based developer
Embodiment 12 3A Dissolving
Embodiment 13 5A Do not dissolve
(embodiment 14)
To internal volume is monomer 2g and the vinyl acetic monomer 2.67g that adds in the glass voltage-resistant reactor of 30mL by embodiment 1 gained.Then, interpolation is as IPP (peroxy dicarbonate isopropyl esters) 0.076g of polymerization starter.Carry out freezing degassing tube sealing afterwards in the system, make its in the constant temperature vibrating trough (40 ℃) carry out polymerization 19 hours.After the polymerization, reaction soln is splashed in the hexane, make after the polymkeric substance redeposition, 100 ℃ of vacuum-dryings of implementing 21 hours.As a result, obtain having the amorphism polymkeric substance of fluorine-containing ring structure (below, be called polymer 6A) 1.37g on the main chain.Through with THF as the PSt conversion molecular weight that GPC measured of solvent being: number-average molecular weight (Mn) is 5700, weight-average molecular weight is (Mw) 10500, Mw/Mn=1.84.It is at room temperature for the polymkeric substance of white powder.Resulting polymkeric substance dissolves in acetone, THF, methyl alcohol and R225.
(embodiment 15,16)
Make that synthetic polymkeric substance 3A, each 1g of 6A are dissolved in respectively among PGMEA (propylene glycol monomethyl ether acetate) 9g in embodiment 4 and 14, the PTFE system membrane filtration with aperture 0.2 μ m obtains etchant resist protection film composition.
The above-mentioned etchant resist protection of rotary coating film composition on silicon substrate, 90 seconds heat treated are carried out at 100 ℃ in the coating back, form the etchant resist protective membrane of thickness 0.21 μ m.The light penetration of the etchant resist protective membrane of gained and the contact angle of water is shown in table 3 like this.
[table 3]
Polymer 193nm transmittance (%) Contact angle (degree)
Embodiment 15 3A 99.3 74
Embodiment 16 6A 98.5 74
(embodiment 17,18) are to the deliquescent mensuration of alkaline-based developer
Synthetic polymer 3A in embodiment 4 and 14, each 1g of 6A are dissolved among PGMEA (propylene glycol monomethyl ether acetate) 9g, use the PTFE system membrane filtration of aperture 0.2 μ m, be coated on the silicon substrate again.Make the silicon substrate that is coated with polymkeric substance be immersed in 2.38% tetramethylammonium hydroxide aqueous solution and the ultrapure water 30 seconds, estimate solvability.The results are shown in table 4.
[table 4]
Polymer Solvability to alkaline-based developer Solvability to ultrapure water
Embodiment 17 3A Dissolving Do not dissolve
Embodiment 18 6A Dissolving Do not dissolve
The possibility of utilizing on the industry
Fluoropolymer of the present invention also can utilize such as ion exchange resin, amberplex, fuel cell, various battery material, optical fiber, electronics parts, hyaline membrane material, plastic film for agricultural use, adhesive, fiber material, weatherability coating etc. except using the purposes of base polymer with base polymer and etchant resist diaphragm as photoresist.

Claims (5)

1. the fluorine-containing diene shown in the following formula (1)
CF 2＝CFCH 2CH(C(R 1)(R 2)(OH))CH 2CH＝CH 2 (1)
In the formula, R 1And R 2Represent independently that respectively fluorine atom or carbonatoms are smaller or equal to 5 fluoroalkyl.
2. fluorine-containing diene as claimed in claim 1, its feature also is, R 1And R 2Be trifluoromethyl.
3. fluoropolymer (A) is characterized in that, have by claim 1 or 2 described fluorine-containing diene cyclopolymerizations and monomeric unit.
4. the manufacture method of fluoropolymer (A) is characterized in that, cyclopolymerization claim 1 or 2 described fluorine-containing diene.
5. the protective membrane composition of etchant resist is characterized in that, contains the solvent of described fluoropolymer of claim 3 (A) and dissolving or dispersion fluoropolymer (A).
CNB2004800315383A 2003-10-31 2004-10-29 Fluorinated compound, fluoropolymer and process for its production Expired - Fee Related CN100384799C (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002065212A1 (en) * 2001-02-09 2002-08-22 Asahi Glass Company, Limited Resist composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002065212A1 (en) * 2001-02-09 2002-08-22 Asahi Glass Company, Limited Resist composition

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