WO2022124182A1 - 含フッ素重合体の製造方法及び組成物 - Google Patents
含フッ素重合体の製造方法及び組成物 Download PDFInfo
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- WO2022124182A1 WO2022124182A1 PCT/JP2021/044211 JP2021044211W WO2022124182A1 WO 2022124182 A1 WO2022124182 A1 WO 2022124182A1 JP 2021044211 W JP2021044211 W JP 2021044211W WO 2022124182 A1 WO2022124182 A1 WO 2022124182A1
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- Prior art keywords
- fluorine
- formula
- group
- containing monomer
- represented
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 363
- 239000011737 fluorine Substances 0.000 title claims abstract description 337
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 336
- 229920000642 polymer Polymers 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 206
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 56
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 34
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 30
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
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- 238000000746 purification Methods 0.000 claims abstract description 19
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- 238000000034 method Methods 0.000 claims abstract description 11
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- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 9
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 9
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- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 125000000486 o-cresyl group Chemical group [H]C1=C([H])C(O*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- VWQXLMJSFGLQIT-UHFFFAOYSA-N prop-2-enoyl bromide Chemical compound BrC(=O)C=C VWQXLMJSFGLQIT-UHFFFAOYSA-N 0.000 description 1
- HJBYJZCUFFYSGA-UHFFFAOYSA-N prop-2-enoyl fluoride Chemical compound FC(=O)C=C HJBYJZCUFFYSGA-UHFFFAOYSA-N 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical class C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- JRHMNRMPVRXNOS-UHFFFAOYSA-N trifluoro(methoxy)methane Chemical compound COC(F)(F)F JRHMNRMPVRXNOS-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
- C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
Definitions
- the present disclosure relates to a method for producing a fluorine-containing polymer and a composition.
- the fluorine-containing polymer has water repellency, oil repellency, low water absorption, heat resistance, weather resistance, corrosion resistance, transparency, photosensitive, low refractive index, low dielectric property, etc. Due to its characteristics, it is being used or developed in a wide range of application fields, mainly in the field of advanced materials. In particular, when it comes to coating applications, antireflection films that apply low refractive index and transparency of visible light, optical devices that apply transparency in the high wavelength band (optical communication wavelength band), and ultraviolet regions (especially vacuum ultraviolet). Active research and development is being carried out in fields such as resist materials that apply transparency in the wavelength range. As a polymer design common to these application fields, by introducing as much fluorine as possible, transparency at each wavelength used is realized, while adhesion to the substrate and high glass transition point (hardness) are realized. It is something to try.
- Patent Document 1 describes a polymerizable monomer represented by the following formula (6).
- R 1p is a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorine-containing alkyl group (the fluorine-containing alkyl group is a linear or branched chain and may contain a cyclic structure).
- R 2p is a divalent to trivalent organic group, wherein the organic group is an aliphatic hydrocarbon group (the aliphatic hydrocarbon group is a linear or branched chain. , Aromatic ring groups, or groups selected from their composite substituents, wherein some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups.
- 3p is a hydrogen atom, a hydrocarbon group, a fluorine-containing alkyl group (the fluorine-containing alkyl group is a linear or branched chain and may contain a cyclic structure), or an aromatic ring group, and the hydrocarbon group is used.
- M is an integer of 1 to 2. Represents. When m is 2, the two R3p can be the same or different from each other.)
- the polymerizable monomer represented by the formula (6) has a (CF 3 ) 2 (OR 3p ) C-site derived from hexafluoroacetone, has a high fluorine content, and is well-balanced in the same molecule. It is a monomeric compound that has succeeded in having a polar group.
- the polymerizable monomer is also excellent in polymerizable property, and the fluorine-containing polymer obtained by polymerizing the polymerizable monomer has the transparency brought about by the fluorine atom, the adhesion brought about by the polar group, and the processability. It is known that it has excellent physical properties as an antireflection film material, an optical device material, a resist material, and the like.
- An object of the present disclosure is to provide a method for producing a fluorine-containing polymer having little variation in weight average molecular weight from lot to lot.
- the present inventors have conducted diligent studies in view of the above problems. As a result, it was found that the side reaction product generated when the polymerizable monomer was produced was a cause of the variation in the weight average molecular weight of the fluorine-containing polymer for each lot, and the present disclosure was reached.
- the method for producing a fluorinated polymer of the present disclosure is a method for producing a fluorinated polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2). At least one selected from the group consisting of an unsaturated carboxylic acid, an ester of the unsaturated carboxylic acid, an acid fluoride of the unsaturated carboxylic acid, and an anhydride of the unsaturated carboxylic acid in the diol represented by the formula (3).
- the fluorine-containing monomer represented by the above formula (5) is removed from the above composition, and the fluorine-containing monomer represented by the above formula (4) is used as a reference.
- a polymerization reaction is carried out using the above composition to obtain a fluorine-containing polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2). It is characterized by including.
- R 1 and R 2 are independently hydrogen atom, methyl group, ethyl group and n-propyl group, respectively. , Iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group or t-butyl group, and R 3 and R 4 are independently hydrogen atoms, methyl groups or ethyl groups, respectively, and R 5 Is a hydrogen atom or a trifluoromethyl group, and R6 is a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group.
- the standard deviation of the weight average molecular weight of the obtained fluorine-containing polymer is divided by the average value of the weight average molecular weight of the fluorine-containing polymer. It is preferable to synthesize the fluorine-containing polymer so that a certain relative standard deviation is 0.10 to 1.10.
- R5 is a trifluoromethyl group.
- R 3 and R 4 are hydrogen atoms.
- R 1 is a methyl group or an iso-propyl group and R 2 is a hydrogen atom.
- the polymerization reaction in the above polymerization step is preferably a radical polymerization reaction.
- composition of the present disclosure is expressed in parts per million based on the fluorine-containing monomer represented by the following formula (4) and the fluorine-containing monomer represented by the above formula (4). It is characterized by containing 1500 ppm or less of a fluorine-containing monomer represented by the following formula (5).
- R 1 and R 2 are independently hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group and iso-butyl group, respectively.
- Sc-butyl group or t-butyl group, R 3 and R 4 are independent hydrogen atoms, methyl or ethyl groups, R 5 is a hydrogen atom or trifluoromethyl group, and R 6 is hydrogen. Atomic, chlorine atom, methyl group or trifluoromethyl group.
- R5 is a trifluoromethyl group.
- R 3 and R 4 are hydrogen atoms.
- R 1 is a methyl group or an iso-propyl group and R 2 is a hydrogen atom.
- composition of the present disclosure preferably further contains a fluorine-containing monomer represented by the above formula (4) and another monomer other than the fluorine-containing monomer represented by the above formula (5). ..
- composition of the present disclosure preferably further contains an organic solvent.
- the present disclosure can provide a method for producing a fluorine-containing polymer having little variation in weight average molecular weight from lot to lot. Further, since the composition of the present disclosure contains a small amount of the fluorine-containing monomer represented by the formula (5), the composition of the present disclosure contains a small amount of variation in the weight average molecular weight from lot to lot. Fluorine polymers can be produced.
- the method for producing a fluorine-containing polymer of the present disclosure is a method for producing a fluorine-containing polymer including a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2). It includes a fluorine monomer synthesis step, a fluorine-containing monomer purification step, and a polymerization step. In the fluorine-containing monomer synthesis step, an unsaturated carboxylic acid, an ester of the unsaturated carboxylic acid, an acid halide of the unsaturated carboxylic acid, and an anhydride of the unsaturated carboxylic acid are added to the diol represented by the following formula (3).
- At least one selected from the group consisting of the above is reacted, and the fluorine-containing monomer represented by the following formula (4), which is the main reaction product, and the following formula (5), which is the side reaction product, are represented.
- a composition containing a fluorine-containing monomer is obtained.
- the fluorine-containing monomer purification step the fluorine-containing monomer represented by the formula (5) is removed from the composition obtained in the fluorine-containing monomer synthesis step, and the fluorine-containing monomer represented by the formula (4) is removed.
- the content of the fluorine-containing monomer represented by the formula (5) is 1500 ppm or less, expressed as a mass percentage based on the monomer.
- a polymerization reaction is carried out using the composition after the fluorine-containing monomer purification step, and the fluorine-containing weight including the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2). Combine.
- R 1 and R 2 are independently hydrogen atom, methyl group, ethyl group and n-propyl group, respectively. , Iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group or t-butyl group, and R 3 and R 4 are independently hydrogen atoms, methyl groups or ethyl groups, respectively, and R 5 Is a hydrogen atom or a trifluoromethyl group, and R6 is a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group.
- the fluorine-containing monomer represented by the formula (4), which is the main reaction product, and the formula (5), which is the side reaction product are used in the process of synthesizing the fluorine-containing monomer.
- the represented fluorine-containing monomer is produced.
- the fluorine-containing monomer represented by the formula (5), which is a side reaction product causes the weight average molecular weight of the fluorine-containing polymer obtained in the subsequent step to vary from lot to lot.
- the fluorine-containing monomer represented by the formula (5) which is a side reaction product, is removed from the composition, and the formula ( It is expressed in parts per million based on the fluorine-containing monomer represented by 4), and the content of the fluorine-containing monomer represented by the formula (5) is 1500 ppm or less. Therefore, when the fluorine-containing polymer is produced by the method for producing a fluorine-containing polymer of the present disclosure, it is possible to reduce the variation in the weight average molecular weight of the fluorine-containing polymer for each lot.
- a fluorine-containing monomer synthesis step In the method for producing a fluorine-containing polymer of the present disclosure, first, a fluorine-containing monomer synthesis step is performed.
- At least one selected from the above hereinafter, also referred to as "unsaturated carboxylic acid and the like" is reacted.
- R 1 and R 2 are independently hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group and n-butyl group, respectively.
- Iso-butyl group, sec-butyl group or t-butyl group, R 3 and R 4 are independently hydrogen atom, methyl group or ethyl group, and R 5 is hydrogen atom or trifluoromethyl group.
- R 6 is a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group.
- the diol represented by the formula (3) has the same molecule of two alcohol moieties, a fluorine-containing alcohol moiety containing a fluorine atom and an alkyl alcohol moiety not having a fluorine atom.
- the fluorine-containing alcohol moiety is electron-withdrawing and has a bulky trifluoromethyl group. It is presumed that the fluorine-containing alcohol moiety is electron-withdrawing and its steric effect suppresses the nucleophilicity of the unshared electron pair at the alcohol moiety, and addition reactions such as unsaturated carboxylic acids are unlikely to occur. ) Is synthesized as the main reaction product.
- the fluorine-containing alcohol moiety remains in the fluorine-containing monomer represented by the formula (4).
- a slight addition reaction such as unsaturated carboxylic acid occurs. Therefore, when synthesizing the fluorine-containing monomer represented by the formula (4), the fluorine-containing monomer represented by the formula (5) is synthesized as an unavoidable side reaction product.
- the composition obtained in the fluorine-containing monomer synthesis step is represented by the fluorine-containing monomer represented by the formula (4), which is the main reaction product, and the formula (5), which is the side reaction product. Fluorine-containing monomer is included.
- an unsaturated carboxylic acid or the like is further added to the addition site of the unsaturated carboxylic acid or the like of the fluorine-containing monomer represented by the formula (4), and the following formula (7) is added.
- the fluorine-containing monomer represented by may be synthesized.
- the composition obtained in the fluorine-containing monomer synthesis step may contain a fluorine-containing monomer represented by the formula (7).
- R 1 and R 2 are independently hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group and sec-butyl group.
- R 3 and R 4 are independently hydrogen atom, methyl group or ethyl group
- R 5 is hydrogen atom or trifluoromethyl group
- R 6 is hydrogen atom, chlorine atom, respectively. Methyl group or trifluoromethyl group.
- an addition reaction such as an unsaturated carboxylic acid is unlikely to occur in the fluorine-containing alcohol moiety containing a fluorine atom, so that it is not suitable only in the fluorine-containing alcohol moiety containing a fluorine atom. Almost no compound such as saturated carboxylic acid has undergone an addition reaction. Further, even if such a compound is generated, an addition reaction such as an unsaturated carboxylic acid rapidly occurs at the alkyl alcohol moiety that does not have a highly reactive fluorine atom, and the fluorine-containing compound represented by the formula (5) is contained. The monomer is synthesized.
- an addition reaction such as an unsaturated carboxylic acid occurs only in the fluorine-containing alcohol moiety containing a fluorine atom in the diol represented by the formula (3). Alcohol is hardly detected.
- R 1 is preferably a methyl group or an iso-propyl group
- R 2 to R 4 are preferably hydrogen atoms
- 5 is preferably a trifluoromethyl group.
- At least one selected from the group consisting of unsaturated carboxylic acid, ester of unsaturated carboxylic acid, acid halide of unsaturated carboxylic acid and anhydride of unsaturated carboxylic acid used in the fluorine-containing monomer synthesis step is methacryl.
- examples thereof include agents, acrylicizing agents and other esterifying agents.
- Examples of the methacrylic acid agent used in the fluorine-containing monomer synthesis step include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate and sec methacrylate.
- -Methacrylic acid esters such as butyl and tert-butyl methacrylate, acid halides such as chloride, methacrylic acid fluoride and methacrylic acid bromide, methacrylic acid anhydrides, methacrylic acid and the like can be exemplified.
- Examples of the acrylate agent used in the fluorine-containing monomer synthesis step include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, and sec acrylate.
- -Acrylic acid esters such as butyl and tert-butyl acrylic acid, acid halides such as acrylic acid chloride, acrylic acid fluoride and acrylic acid bromide, acrylic acid anhydrides, acrylic acid and the like can be exemplified.
- esterifying agents used in the fluorine-containing monomer synthesis step include carboxylic acid esters not contained in the methacrylic acid and acrylicizing agents, acid halides such as carboxylic acid chloride, carboxylic acid anhydrides, and carboxylic acids. Can be exemplified.
- a methacrylic acid agent it is preferable to use a methacrylic acid agent, and more preferably to use a methacrylic anhydride and / or a methacrylic acid chloride.
- the diol represented by the formula (3) is composed of a group consisting of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, an acid halide of the unsaturated carboxylic acid, and an anhydride of the unsaturated carboxylic acid. Acids and bases may be added as needed when reacting at least one selected species.
- the diol represented by the formula (3) is composed of a group consisting of an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, an acid halide of the unsaturated carboxylic acid, and an anhydride of the unsaturated carboxylic acid.
- the reaction conditions for reacting at least one selected species are preferably 30 to 130 ° C. for 0.5 to 8 hours.
- the amount of the fluorine-containing monomer represented by the formula (5) as a by-reactant varies depending on the type of unsaturated carboxylic acid and the like, the reaction temperature and the reaction time. If the amount of unsaturated carboxylic acid or the like used is too small, the amount of fluorine-containing monomer represented by the formula (5) can be reduced, but the unreacted diol represented by the formula (3) can be reduced. Since a large amount remains, it is necessary to separate the fluorine-containing monomer represented by the formula (4) and the diol represented by the formula (3).
- the amount of the unsaturated carboxylic acid used is too large, the amount of the fluorine-containing monomer represented by the formula (5) is increased.
- homopolymers such as unsaturated carboxylic acids may be produced. For this reason, it is selected from the group consisting of the diol represented by the formula (3) used, an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid, an acid halide of the unsaturated carboxylic acid, and an anhydride of the unsaturated carboxylic acid.
- a preferable compound as the fluorine-containing monomer represented by the formula (4) obtained in the fluorine-containing monomer synthesis step is methacrylic acid 5, which is a fluorine-containing monomer represented by the following formula (4-1).
- 5,5-Trifluoro-4-hydroxy-4-trifluoromethylpentane-2-yl and 1,1,1-trifluoromethacrylate which is a fluorine-containing monomer represented by the following formula (4-2) -2-hydroxy-2-trifluoromethylheptane-4-yl can be mentioned.
- a fluorine-containing monomer purification step is performed.
- the fluorine-containing monomer represented by the formula (5) is removed from the composition obtained by the fluorine-containing monomer synthesis step, and the fluorine-containing monomer represented by the formula (4) is removed.
- the content of the fluorine-containing monomer represented by the formula (5) is 1500 ppm or less, expressed as a mass percentage based on the monomer.
- the content of the fluorine-containing monomer represented by the formula (5) is preferably 450 ppm or less, more preferably 200 ppm or less. Further, the content of the fluorine-containing monomer represented by the formula (5) is more preferably 10 ppm or more.
- the fluorine-containing monomer represented by the formula (5) causes the weight average molecular weight of the fluorine-containing polymer obtained in the subsequent step to vary from lot to lot.
- the fluorine-containing monomer represented by the formula (4) is represented by the mass percentage based on the fluorine-containing monomer represented by the formula (4).
- the method for removing the fluorine-containing monomer represented by the formula (5) from the composition is not particularly limited, but for example, a known method such as column chromatography, precision distillation or crystallization can be used. These methods may be combined in order to obtain a fluorine-containing monomer represented by the formula (4) having high purity. Hereinafter, each method will be described in detail.
- the fluorine-containing monomer represented by the formula (5) is removed from the composition by filling a general columnar tubular base material with a filler and flowing the composition in a mobile phase using an organic solvent.
- the filler is not particularly limited, and silica gel or alumina gel is preferable, and alumina gel is more preferable.
- As the filler one type may be used, or two or more types may be used.
- the mobile phase is not particularly limited, and general organic solvents such as hexane, heptane, toluene and ethyl acetate can be used. Further, one type of mobile phase may be used, or two or more types may be used.
- the temperature at which the column chromatograph is performed is preferably in the range of 0 ° C to 40 ° C, more preferably in the range of 20 ° C to 30 ° C.
- Increasing the amount (height) of the filler added requires a lot of time, but increasing the amount (height) of the filler added improves the degree of separation.
- the height of the filler is preferably 5 cm to 15 cm.
- the fluorine-containing monomer represented by the formula (4) may cause a polymerization reaction.
- a polymerization inhibitor may be added to the composition.
- oxygen may be introduced into the distillation column.
- the polymerization inhibitor is not particularly limited, but is o-cresol, m-cresol, p-cresol, 6-t-butyl-2,4-xylenol, 2,6-di-t-butyl-p-cresol, hydroquinone.
- polymerization prohibitive agents examples include N, N'-di-2-naphthyl-p-phenylenediamine (trade name, non-flex F) and N, N-diphenyl-p-phenylenediamine (trade name, non-flex F) manufactured by Seiko Kagaku Co., Ltd.
- non-flex H 4,4'-bis (a, a-dimethylbenzyl) diphenylamine (trade name, non-flex DCD), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) ) (Product name, non-flex MBP), N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine (trade name, Ozonone 35), or ammonium N-nitrosophenyl manufactured by Wako Pure Chemical Industries, Ltd. Hydroxylamine (trade name, Q-1300) or N-nitrosophenylhydroxyamine aluminum salt (trade name, Q-1301) can be exemplified.
- the amount of the polymerization inhibitor used in the precision distillation is not particularly limited, but is 0.01 part by mass or more with respect to 100 parts by mass of the fluorine-containing monomer represented by the formula (4) based on before the precision distillation. It is preferably 5 parts by mass or less, and more preferably 0.01 parts by mass or more and 1 part by mass or less.
- the amount of the polymerization inhibitor is less than 0.01 parts by mass with respect to 100 parts by mass of the fluorine-containing monomer represented by the formula (4), the fluorine-containing monomer represented by the formula (4) is polymerized. It becomes difficult to prevent.
- the polymerization inhibitor exceeds 5 parts by mass with respect to 100 parts by mass of the fluorine-containing monomer represented by the formula (4), the effect of preventing the polymerization of the fluorine-containing monomer represented by the formula (4) is the upper limit. It becomes difficult to improve cost effectiveness.
- the content of the fluorine-containing monomer represented by the formula (4) in the composition can be measured by gas chromatography.
- the fluorine-containing monomer represented by the formula (5) can be removed from the composition by using crystallization.
- Crystallization is an operation in which a composition is dissolved in a good solvent, a poor solvent is added, or the temperature is lowered to precipitate a fluorine-containing monomer represented by the formula (4), and crystals are grown. be.
- the type of solvent used for crystallization is not particularly limited as long as the fluorine-containing monomer represented by the formula (4) is easily soluble or insoluble, but alcohols, nitriles, ketones and amides are not particularly limited. Classes, sulfoxides, ethers, hydrofluorocarbons, hydrofluoroethers, hydrocarbons, aromatic hydrocarbons or water.
- Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol and the like.
- Examples of nitriles include acetonitrile, benzonitrile and the like.
- Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone and the like.
- Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone and the like.
- Examples of sulfoxides include dimethyl sulfoxide and the like.
- Examples of ethers include diethyl ether, methyl-t-butyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran and the like.
- Examples of hydrofluorocarbons include trifluoromethane, difluoromethane, 1,1,1,2-tetrafluoroethane, 1,1,1-tetrafluoroethane, 1,1-difluoroethane, 1,1,1,2,3.
- hydrofluoroethers include methyl 1,1,2,2,2-pentafluoroethyl ether, methyltrifluoromethyl ether, methyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2.
- hydrocarbons examples include butane, pentane, hexane, heptane, octane, nonane, decane and the like.
- aromatic hydrocarbons examples include benzene, toluene, xylene, mesitylene, perfluorobenzene and the like. It is preferable to use at least one compound selected from these solvents as a good solvent or a poor solvent.
- the amount of the solvent for crystallization is 50 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the fluorine-containing monomer represented by the formula (4), based on the amount before crystallization. It is preferably 100 parts by mass or more, and more preferably 1000 parts by mass or less.
- the amount of the solvent is less than 50 parts by mass with respect to 100 parts by mass of the fluorine-containing monomer represented by the formula (4), the slurry of the fluorine-containing monomer represented by the formula (4) precipitated by crystallization. It is difficult to stir and mix.
- the content of the fluorine-containing monomer represented by the formula (4) in the composition can be measured by gas chromatography.
- the fluorine-containing monomer represented by the formula (4) after the fluorine-containing monomer purification step and the fluorine-containing monomer represented by the formula (4) are expressed in parts per million.
- the composition containing 1500 ppm or less of the fluorine-containing monomer represented by the formula (5) is also the composition of the present disclosure.
- another single amount other than the fluorine-containing monomer represented by the formula (4) and the fluorine-containing monomer represented by the formula (5) is added to the composition.
- the body and organic solvents may be added.
- a composition containing these is also the composition of the present disclosure.
- a polymerization step is performed.
- the compound containing the repeating unit represented by the formula (1) is contained.
- the compound containing the repeating unit represented by the formula (1) is contained.
- Use as a fluorine polymer since the composition after the fluorine-containing monomer purification step contains the fluorine-containing monomer represented by the formula (5) that cannot be completely removed, the fluorine-containing simple substance represented by the formula (5) is contained. The monomer also polymerizes. Therefore, the obtained fluorine-containing polymer contains a repeating unit represented by the formula (2).
- the fluorine-containing monomer represented by the formula (4) is polymerized using the composition having a low content of the fluorine-containing monomer represented by the formula (5), so that the obtained fluorine-containing weight is obtained.
- the variation in the weight average molecular weight of the fluorine-containing polymer for each lot becomes small.
- an unsaturated carboxylic acid or the like which has undergone an addition reaction to a fluorine-containing alcohol moiety containing a fluorine atom of the fluorine-containing monomer represented by the formula (5) may be polymerized. Therefore, the obtained fluorine-containing polymer may contain a repeating unit represented by the following formula (8).
- R 1 and R 2 are independently hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group and sec-butyl group.
- R 3 and R 4 are independently hydrogen atom, methyl group or ethyl group
- R 5 is hydrogen atom or trifluoromethyl group
- R 6 is hydrogen atom, chlorine atom, respectively. Methyl group or trifluoromethyl group.
- an unsaturated carboxylic acid or the like which has undergone an addition reaction to an alkyl alcohol moiety which does not have a fluorine atom of the fluorine-containing monomer represented by the formula (5), and a fluorine-containing alcohol moiety containing a fluorine atom.
- both unsaturated carboxylic acids and the like that have undergone an addition reaction to the above may polymerize. Therefore, the obtained fluorine-containing polymer may contain such a repeating unit.
- a composition after the fluorine-containing monomer purification step contains a fluorine-containing monomer represented by the formula (4) and another monomer other than the fluorine-containing monomer represented by the formula (5).
- the polymerization reaction may be carried out using the composition.
- Examples of the monomer other than the fluorine-containing monomer represented by the formula (4) and the fluorine-containing monomer represented by the formula (5) include the following monomers. That is, a monomer having a hexafluoroisopropanol group (-C (CF 3 ) 2 OH), acrylic acid esters, methacrylic acid esters, fluoroacrylic acid esters, fluoromethacrylic acid esters, styrenes, etc.
- Fluorostyrenes vinyl ethers, fluorinated vinyl ethers, allyl ethers, fluorinated allyl ethers, unsaturated amides, olefins, fluorinated olefins, norbornene compounds, fluorinated norbornene compounds, vinylsilanes, vinylsulfonic acids or Vinyl sulfonic acid ester Acrylic acid, maleic acid methacrylate, maleic anhydride, fumaric acid, sulfur dioxide and the like.
- a monomer containing an acid-degradable group may be used as another monomer.
- a fluorine-containing polymer using a monomer containing an acid-decomposable group
- an electromagnetic wave or an electron beam having a wavelength of 300 nm or less is formed on a resist film formed on a substrate.
- Acid-degradable groups are decomposed by exposure to high-energy rays such as, and acid is generated in the resist film. With this acid, the solubility of the resist film in the exposed portion in the alkaline developer in development can be improved.
- a monomer having a lactone structure may be used as another monomer.
- a fluorine-containing copolymer having a lactone structure By producing a fluorine-containing copolymer using a monomer having a lactone structure, the adhesion between the resist film containing the fluorine-containing copolymer and the substrate is improved when the fluorine-containing polymer is used as a resist. Can be made to. Further, when the fluorine-containing copolymer is used in the composition for forming the upper layer film and used as the upper layer film on the resist pattern, not only the adhesion with the resist pattern of the lower layer is improved, but also the adhesion with the developer during development is improved. It is possible to increase the affinity and obtain a high-definition resist pattern.
- One of these other monomers may be added, or two or more thereof may be added.
- Examples of the monomer having a hexafluoroisopropanol group include the following monomers.
- R 7 is a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group, and the hydrogen atom of the hydroxyl group may be substituted with a protective group.
- acrylic acid esters examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and 2-hydroxyl.
- Examples thereof include ethyl acrylate, 2-hydroxypropyl acrylate tert-butyl acrylate, 3-oxocyclohexyl acrylate, adamantyl acrylate, methyl adamantyl acrylate, ethyl adamantyl acrylate, hydroxyadamantyl acrylate, cyclohexyl acrylate, and tricyclodecanyl acrylate.
- methacrylic acid esters examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and 2-hydroxyl methacrylate.
- Examples thereof include ethyl methacrylate, 2-hydroxypropyl methacrylate, tert-butyl methacrylate, 3-oxocyclohexyl methacrylate, adamantyl methacrylate, methyl adamantyl methacrylate, ethyl adamantyl methacrylate, hydroxyadamantyl methacrylate, cyclohexyl methacrylate, tricyclodecanyl methacrylate and the like. ..
- the fluorine-containing acrylic acid ester and the fluorine-containing methacrylic acid ester may be an acrylic acid ester or a methacrylic acid ester containing an alkyl group having a fluorine atom or a fluorine atom at the ⁇ -position of the acrylic structure, and the ester structure may be formed. It may be an acrylic acid ester or a methacrylic acid ester containing a fluorine atom or an alkyl group having a fluorine atom.
- an alkyl group having a fluorine atom or a fluorine atom may be contained in both the ⁇ -position and the ester moiety of the acrylic structure. Further, a cyano group may be introduced at the ⁇ -position of the acrylic structure.
- alkyl group having a fluorine atom to be introduced at the ⁇ -position of the acrylic structure in the fluorine-containing acrylic acid ester or the fluorine-containing methacrylic acid ester include a trifluoromethyl group, a trifluoroethyl group, and nonafluoro-n-.
- a butyl group can be exemplified.
- the ester structure may have a fluorinated alkyl group such as a perfluoroalkyl group or a fluoroalkyl group. Further, the cyclic structure and the fluorine atom may coexist in the ester structure.
- the cyclic structure has a fluorine atom, a trifluoromethyl group, a fluorine-containing benzene ring having a hexafluoroisopropyl hydroxyl group, a fluorine-containing cyclopentane ring, a fluorine-containing cyclohexane ring, a fluorine-containing cycloheptane ring, or the like.
- the ester structure may be a t-butyl ester group having a fluorine atom.
- fluoroacrylic acid esters examples include 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 1,1,1,3,3,3-hexafluoroisopropyl.
- fluorine-containing methacrylic acid esters examples include 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate.
- styrenes and fluorinated styrenes include styrene, hydroxystyrene, fluorinated styrene and the like.
- the fluorinated styrene may be pentafluorostyrene, trifluoromethylstyrene, bistrifluoromethylstyrene or the like as styrene in which hydrogen in the aromatic ring is substituted with a fluorine atom or a trifluoromethyl group. Further, styrene may be obtained by substituting hydrogen in the aromatic ring with a hexafluoroisopropanol group or a hexafluoroisopropanol group in which the hydroxyl group thereof is protected with a protecting group.
- styrene in which a halogen, an alkyl group and a fluorine-containing alkyl group are bonded to the ⁇ -position, styrene containing a perfluorovinyl group and the like may be used.
- Vinyl ethers, fluorine-containing vinyl ethers, allyl ethers, and fluorine-containing allyl ethers have a hydroxyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, or a hydroxybutyl group in the structure. May be good. Further, these compounds may contain a cyclohexyl group, a norbornyl group, an aromatic ring, or cyclic vinyls or allyl ethers having a hydrogen or carbonyl bond in the cyclic structure thereof, and have these. Part or all of the hydrogen atom may be replaced with a fluorine atom.
- unsaturated amides include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone acrylamide and the like.
- olefins examples include ethylene, propylene, isobutene, cyclopentene, cyclohexene and the like.
- fluorine-containing olefins examples include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, hexafluoroisobutene and the like.
- the monomer having a norbornene moiety may have one or more norbornene moieties in the monomer, and the hydrogen atom of the norbornene moiety may be substituted with a functional group containing a fluorine atom.
- Examples of such a monomer include cyclopentadiene and norbornene compounds synthesized by a Diels-Alder addition reaction between cyclopentadiene and an unsaturated compound.
- the unsaturated compounds used when synthesizing the norbornene compound include acrylic acid, methacrylic acid, ⁇ -fluoroacrylic acid, ⁇ -trifluoromethylacrylic acid, acrylic acid ester, methacrylic acid ester, fluorine-containing acrylic acid ester, and the like.
- the acid-degradable group can be used without particular limitation as long as it is hydrolyzed by an acid generated from a photoacid generator contained in the resist and desorbed from the fluoropolymer. ..
- a monomer having an acid-decomposable group represented by the following formula (9) or formula (10) is preferable.
- R 8 , R 9 , R 10 , and R 12 are independently linear alkyl having 1 to 25 carbon atoms and branched chain or cyclic alkyl having 3 to 25 carbon atoms, respectively.
- a group, in which a part or all of the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom or a hydroxyl group.
- R 8 , R 9 , and R 10 Any two of them may be bonded to form a ring.
- R 11 is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, and a branched chain or cyclic alkyl group having 3 to 25 carbon atoms. , A part or all of the hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom or a hydroxyl group. The dotted line is a bond.
- acid-decomposable groups represented by the formulas (9) and (10) include the acid-decomposable groups shown below.
- the dotted line is a bond.
- the monomer having a lactone structure there are many monocyclic lactone structures such as a group obtained by removing one hydrogen atom from ⁇ -butyrolactone and mevalonic lactone, and a group obtained by removing one hydrogen atom from norbornan lactone.
- a monomer having a cyclic lactone structure and the like can be exemplified.
- the exposure time can be shortened by immersion exposure using water as an exposure medium.
- the surface tension can be reduced, the surface of the upper film can be smoothed, and the film thickness can be made uniform.
- the amount thereof is not particularly limited, but in the fluorinated polymer after polymerization, when all the repeating units contained in the fluorinated polymer are 100 mL%, another monomer is added.
- the ratio of the derived repeating unit is preferably 1 mol% or more and 80 mol% or less, more preferably 5 mol% or more and 70 mol% or less, and further preferably 10 mol% or more and 60 mol% or less.
- the ratio of the repeating unit derived from another monomer is less than 1 mol%, the effect of improving the solubility in the organic solvent expected when the fluoropolymer is used as a resist, and the resist film is formed on the substrate.
- the ratio of the repeating unit derived from another monomer exceeds 80 mol%, the ratio of the repeating unit represented by the formula (1) decreases, and the effect of improving the transparency of the resist film and the solvent solubility are improved. It becomes difficult to obtain the effect of making it.
- the polymerization reaction in the polymerization step is not particularly limited, and may be a radical polymerization reaction, an ionic polymerization reaction, a coordination anionic polymerization reaction, a living anionic polymerization reaction, or a cationic polymerization reaction. Among these, a radical polymerization reaction is preferable.
- the polymerization initiator is not particularly limited as long as the polymerization reaction occurs, but an azo compound, a peroxide compound, or a redox compound can be used. ..
- Examples of the azo compound include azobisisobutyronitrile.
- Examples of the peroxide compound include t-butylperoxypivalate, di-t-butyl peroxide, i-butylyl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, and di-n-propyl peroxide. Examples thereof include dicarbonate, t-butylperoxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide and ammonium persulfate.
- Examples of the redox-based compound are used in combination with an oxidizing agent and a reducing agent, and examples thereof include hydrogen peroxide, persulfate, and cumene hydroperoxide as the oxidizing agent side, and iron (II) ion salt and copper as the reducing agent side.
- Ion salts, hydrogen peroxide, triethylamine and the like can be mentioned.
- a polymerization solvent may be used.
- the polymerization solvent is not particularly limited as long as it does not inhibit the radical polymerization reaction, and may be an organic solvent or water.
- the organic solvent include hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, ether solvents, cyclic ether solvents, freon solvents, aromatic solvents and the like. Only one kind of these solvents may be used, or two or more kinds of these solvents may be used in combination.
- ester solvent examples include acetic acid, n-butyl acetate and the like.
- ketone solvent examples include acetone, methyl isobutyl ketone and the like.
- hydrocarbon solvent examples include toluene, cyclohexane and the like.
- alcohol solvent examples include methanol, isopropyl alcohol, and ethylene glycol monomethyl ether.
- a molecular weight adjusting agent such as mercaptan may be used.
- the reaction temperature in the radical polymerization reaction is appropriately changed depending on the type of the radical polymerization initiator or the radical polymerization initiator, but is preferably 20 ° C. or higher and 200 ° C. or lower, and is preferably 30 ° C. or higher and 140 ° C. or lower. More preferred.
- a known method can be used as a method for removing the organic solvent or water as a medium from the solution or dispersion liquid containing the synthesized fluorine-containing polymer after the polymerization step. Specifically, methods such as reprecipitation, filtration, and heating distilling under reduced pressure can be exemplified.
- the relative standard deviation is a value obtained by dividing the standard deviation of the weight average molecular weight of the obtained fluorine-containing polymer by the average value of the weight average molecular weight of the fluorine-containing polymer.
- the relative standard deviation is more preferably 0.10 to 0.60.
- the "standard deviation of the weight average molecular weight of the obtained fluorine-containing polymer" means the standard deviation of the weight average molecular weight of 6 lots of the fluorine-containing polymer manufactured under the same conditions.
- the weight average molecular weight of the fluorine-containing polymer means a numerical value measured by gel permeation chromatography (GPC) under the following conditions.
- the relative standard deviation is set to 0 by sufficiently removing the fluorine-containing monomer represented by the formula (5) from the composition. It can be 10.10 to 1.10.
- the fluorine-containing polymer thus obtained has little variation in the weight average molecular weight of the fluorine-containing polymer for each lot, the alkali solubility does not change easily when forming a resist pattern using the fluorine-containing polymer. , It becomes easy to adjust the exposure and development conditions. Further, when forming a fine resist pattern, unevenness is less likely to occur in the pattern obtained after the developing step.
- the weight average molecular weight of the fluorine-containing polymer varies from lot to lot, unevenness may occur in the pattern obtained after the development step when forming a fine resist pattern using the fluorine-containing polymer. ..
- the fluorinated polymer produced by the method for producing a fluorinated polymer of the present disclosure has little variation in the weight average molecular weight of the fluorinated polymer for each lot. Therefore, in the formation of a fine resist pattern using the fluorine-containing polymer obtained in the present disclosure, the smoothness of the pattern surface obtained after the developing step becomes good.
- the weight average molecular weight of the obtained fluorine-containing polymer is preferably 5000 to 20000, more preferably 7000 to 12000.
- the obtained fluorine-containing polymer can be used as a component of a resist film or an upper layer film that protects a resist pattern. Further, the resist film and the resist pattern formed by using the obtained fluorine-containing polymer have high transparency and high solvent solubility.
- methacrylic acid 5,5,5-trifluoro-4-hydroxy-4-trifluoromethylpentane-2-yl (fluorine-containing monomer represented by the formula (4-1)) is contained. 3.0 kg of the distillate was produced. The obtained fraction was precisely distilled in an Oldershaw distillation column to obtain 2.76 kg of a fraction having a boiling point of 80 ° C. at a pressure of 0.5 kPa. When the obtained fraction was measured by GC-MS, it was represented by methacrylic acid 5,5,5-trifluoro-4-hydroxy-4-trifluoromethylpentane-2-yl (formula (4-1)). The purity of the fluorine-containing monomer) was 99.8%.
- the separated organic layer was washed twice with 200 g of water, and then the solvent was distilled off by a rotary evaporator. Then, distillation was performed with a distillation apparatus equipped with a Vigreux tube. Fractions at 86 ° C. to 88 ° C. were collected at a reduced pressure of 0.5 kPa to obtain 16 g of oil.
- the oil content measured by GC-MS includes a single amount of fluorine-containing 1,1,1-trifluoro-2- (trifluoromethyl) pentane-2,4-diyl (formula (5-1)) represented by methacrylic acid.
- Body is 96% by mass, unreacted methacrylic acid 5,5,5-trifluoro-4-hydroxy-4-trifluoromethylpentane-2-yl (fluorine-containing single amount represented by the formula (4-1)). Body) was contained in an amount of 2.5% by mass. The oil content was used as a standard sample of methacrylic acid 1,1,1-trifluoro-2- (trifluoromethyl) pentane-2,4-diyl (fluorine-containing monomer represented by the formula (5-1)). did.
- Example 1 ⁇ Polymerization process> At room temperature (about 20 ° C.), 100 g of the raw material composition A was placed in a 500 mL container, and dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., product name V) was charged. -601) 200 g of 2-butanone in which 6.26 g was dissolved was added to prepare a solution of the raw material composition A, and then the mixture was transferred to a dropping funnel. Next, the dropping funnel was separately attached to a 500 mL reactor charged with 100 g of 2-butanone, and the temperature of 2-butanone was raised to 78 ° C.
- the solution of the raw material composition A was gradually added dropwise into the reactor over 2 hours from the dropping funnel under a nitrogen stream. After completion of the dropping, the mixture was kept at a temperature of 78 ⁇ 1 ° C. for 6 hours and then cooled. At that time, the mixture was gradually cooled over 30 minutes until the temperature was lowered to 30 ° C. to obtain a fluorine-containing polymer containing a repeating unit represented by the following formula (1-1).
- the obtained fluorine-containing polymer is the fluorine-containing polymer according to Example 1.
- the weight average molecular weight of the fluorine-containing polymer according to Example 1 in each production was measured. Further, a relative standard deviation (RSD: coefficient standard deviation), which is a numerical value obtained by dividing the standard deviation of the weight average molecular weight of the fluorine-containing polymer by the average value of the weight average molecular weight of the fluorine-containing polymer, was calculated. The results are shown in Table 2.
- reaction solution containing the fluorine-containing polymer was gradually added dropwise to n-heptane adjusted to a temperature of 25 ° C. over 1 hour while stirring, and then further stirred for 1 hour to obtain a slurry of the fluorine-containing polymer. Obtained.
- the obtained slurry was filtered under reduced pressure to obtain a cake. By drying the cake, the powder of the fluorine-containing polymer according to Example 1 was obtained.
- Example 2 to (Example 5) Fluorine-containing polymers according to Examples 2 to 5, respectively, were produced in the same manner as in Example 1 except that the raw material compositions B to E were used instead of the raw material composition A. Then, the weight average molecular weight of the fluorine-containing polymer according to Examples 2 to 5 was measured, and the standard deviation of the weight average molecular weight of the fluorine-containing polymer was divided by the average value of the weight average molecular weight of the fluorine-containing polymer. The relative standard deviation is calculated. The results are shown in Table 2.
- the raw material composition A is 80 g, represented by 3,5-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl methacrylate (formula (11)).
- 20 g of (monomer) is placed in a 500 mL container to dissolve 6.26 g of dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., product name V-601).
- 2-butanone After adding 200 g of 2-butanone to prepare a mixed solution with the raw material composition A, the solution was transferred to a dropping funnel. Next, the dropping funnel was separately attached to a 500 mL reactor charged with 100 g of 2-butanone, and the temperature of 2-butanone was raised to 78 ° C.
- the weight average molecular weight of the fluorine-containing polymer according to Example 6 in each production was measured.
- the relative standard deviation which is a numerical value obtained by dividing the standard deviation of the weight average molecular weight of the fluorine-containing polymer by the average value of the weight average molecular weight of the fluorine-containing polymer, was calculated. The results are shown in Table 2.
- Example 7 The fluorine-containing polymer according to Example 7 was produced in the same manner as in Example 6 except that the raw material composition C was used instead of the raw material composition A. Then, the weight average molecular weight of the fluorine-containing polymer according to Example 7 is measured, and the standard deviation of the weight average molecular weight of the fluorine-containing polymer is divided by the average value of the weight average molecular weight of the fluorine-containing polymer. The deviation was calculated. The results are shown in Table 2.
- Example 8 At room temperature (about 20 ° C.), 95 g of the raw material composition A and 5 g of 1,1,2,2-tetrahydroheptadecafluoro-n-decylacrylate (monomer represented by the formula (12)) are placed in a 500 mL container. After charging, 200 g of 2-butanone in which 6.26 g of dimethyl-2,2'-azobis (2-methylpropionate) was dissolved was added to prepare a mixed solution with the raw material composition A, and then the solution was transferred to a dropping funnel. Next, the dropping funnel was separately attached to a 500 mL reactor charged with 100 g of 2-butanone, and the temperature of 2-butanone was raised to 78 ° C.
- the weight average molecular weight of the fluorine-containing polymer according to Example 8 in each production was measured.
- the relative standard deviation which is a numerical value obtained by dividing the standard deviation of the weight average molecular weight of the fluorine-containing polymer by the average value of the weight average molecular weight of the fluorine-containing polymer, was calculated. The results are shown in Table 2.
- Example 9 The fluorine-containing polymer according to Example 9 was produced in the same manner as in Example 8 except that the raw material composition C was used instead of the raw material composition A. Then, the weight average molecular weight of the fluorine-containing polymer according to Example 9 is measured, and the standard deviation of the weight average molecular weight of the fluorine-containing polymer is divided by the average value of the weight average molecular weight of the fluorine-containing polymer. The deviation was calculated. The results are shown in Table 2.
- Comparative Example 1 The fluorine-containing polymer according to Comparative Example 1 was produced in the same manner as in Example 1 except that the raw material composition F was used instead of the raw material composition A. Then, the weight average molecular weight of the fluorine-containing polymer according to Comparative Example 1 is measured, and the standard deviation of the weight average molecular weight of the fluorine-containing polymer is divided by the average value of the weight average molecular weight of the fluorine-containing polymer. The deviation was calculated. The results are shown in Table 2.
- Comparative Example 2 The fluorine-containing polymer according to Comparative Example 2 was produced in the same manner as in Example 8 except that the raw material composition F was used instead of the raw material composition A. Then, the weight average molecular weight of the fluorine-containing polymer according to Comparative Example 2 is measured, and the standard deviation of the weight average molecular weight of the fluorine-containing polymer is divided by the average value of the weight average molecular weight of the fluorine-containing polymer. The deviation was calculated. The results are shown in Table 2.
- methacrylic acid 1,1,1-trifluoro-2- (trifluoromethyl) pentane-2,4-diyl fluorine-containing monomer represented by the formula (5-1)
- the numerical value of RSD of the fluorine-containing polymer according to Examples 1 to 9 produced by using the raw material composition having a concentration of 1500 ppm or less was a small value.
- the concentration of methacrylic acid 1,1,1-trifluoro-2- (trifluoromethyl) pentane-2,4-diyl (fluorine-containing monomer represented by the formula (5-1)) exceeds 1500 ppm.
- the numerical value of RSD of the fluorine-containing polymer according to Comparative Examples 1 and 2 produced by using the raw material composition F was a large value.
Abstract
Description
当該重合性単量体は重合性にも優れ、当該重合性単量体を重合して得た含フッ素重合体は、フッ素原子によってもたらされる透明性と、極性基によってもたらされる密着性、加工性を併せ持ち、反射防止膜材料、光デバイス材料、レジスト用材料等として優れた物性を有することが知られている。
含フッ素重合体の重量平均分子量がロット毎にバラつくと、含フッ素重合体を用いてレジストパターンを形成する際に、アルカリ溶解性が変わり、そのロット毎で、レジストパターンを形成する際の露光現像条件の調整が必要となることがあり、半導体の生産効率に影響を与えることがある。
また、本開示の組成物は、式(5)で表される含フッ素単量体の含有量が少ないので、本開示の組成物を用いることにより、ロット毎の重量平均分子量のバラつきが少ない含フッ素重合体を製造することができる。
含フッ素単量体合成工程では、下記式(3)で表されるジオールに不飽和カルボン酸、上記不飽和カルボン酸のエステル、上記不飽和カルボン酸の酸ハライド及び上記不飽和カルボン酸の無水物からなる群から選択される少なくとも1種を反応させて、主反応物である下記式(4)で表される含フッ素単量体と、副反応物である下記式(5)で表される含フッ素単量体とを含む組成物を得る。
含フッ素単量体精製工程では、含フッ素単量体合成工程で得られた組成物から式(5)で表される含フッ素単量体を除去し、式(4)で表される含フッ素単量体を基準とする質量百万分率で表して、式(5)で表される含フッ素単量体の含有量を1500ppm以下とする。
重合工程では、含フッ素単量体精製工程後の組成物を用いて重合反応を行い、式(1)で表される繰り返し単位と式(2)で表される繰り返し単位とを含む含フッ素重合体とする。
しかし、本開示の含フッ素重合体の製造方法では、含フッ素単量体精製工程において、副反応物である式(5)で表される含フッ素単量体を組成物から除去し、式(4)で表される含フッ素単量体を基準とする質量百万分率で表して、式(5)で表される含フッ素単量体の含有量を1500ppm以下としている。そのため、本開示の含フッ素重合体の製造方法により、含フッ素重合体を製造すると、ロット毎の含フッ素重合体の重量平均分子量のバラつきを小さくすることができる。
本開示の含フッ素重合体の製造方法では、まず、含フッ素単量体合成工程を行う。
含フッ素単量体合成工程では、下記式(3)で表されるジオールに不飽和カルボン酸、不飽和カルボン酸のエステル、不飽和カルボン酸の酸ハライド及び不飽和カルボン酸の無水物からなる群から選択される少なくとも1種(以下、「不飽和カルボン酸等」とも記載する)を反応させる。
これにより、主反応物である下記式(4)で表される含フッ素単量体と、副反応物である下記式(5)で表される含フッ素単量体とを含む組成物を得ることができる。
含フッ素アルコール部位が電子吸引性であることと、その立体効果によりアルコール部位の非共有電子対の求核性が抑制され、不飽和カルボン酸等の付加反応は起こりにくいと推察され、式(4)で表される含フッ素単量体が主反応物として合成される。
その結果、含フッ素単量体合成工程で得られる組成物には、主反応物である式(4)で表される含フッ素単量体と、副反応物である式(5)で表される含フッ素単量体とが含まれる。
含フッ素単量体合成工程で得られる組成物には、式(7)で表される含フッ素単量体が含まれていてもよい。
そのため、本開示における含フッ素単量体合成工程で得られる組成物には、式(3)で表されるジオールにおいてフッ素原子を含む含フッ素アルコール部位のみに不飽和カルボン酸等の付加反応が起こった化合物はほとんど検知されない。
不飽和カルボン酸等の使用量を少なくしすぎると、式(5)で表される含フッ素単量体の生成量を少なくすることができるが、未反応の式(3)で表されるジオールが多く残るので、式(4)で表される含フッ素単量体と式(3)で表されるジオールとの分離が必要になる。
また、不飽和カルボン酸の使用量を多くしすぎると、式(5)で表される含フッ素単量体の生成量が多くなる。また、不飽和カルボン酸等のホモポリマーが生成することがある。
このような理由から、使用する式(3)で表されるジオールと不飽和カルボン酸、不飽和カルボン酸のエステル、不飽和カルボン酸の酸ハライド及び不飽和カルボン酸の無水物からなる群から選択される少なくとも1種とのモル量割合は、[使用する式(3)で表されるジオールのモル量]:[不飽和カルボン酸、不飽和カルボン酸のエステル、不飽和カルボン酸の酸ハライド及び不飽和カルボン酸の無水物からなる群から選択される少なくとも1種のモル量]=1:0.7~1:1.3であることが好ましい。
次に、本開示の含フッ素重合体の製造方法では、含フッ素単量体精製工程を行う。
含フッ素単量体精製工程では、含フッ素単量体合成工程により得られた組成物から式(5)で表される含フッ素単量体を除去し、式(4)で表される含フッ素単量体を基準とする質量百万分率で表して、式(5)で表される含フッ素単量体の含有量を1500ppm以下とする。
また、式(5)で表される含フッ素単量体の含有量は、450ppm以下であることが好ましく、200ppm以下であることがより好ましい。また、式(5)で表される含フッ素単量体の含有量は、10ppm以上であることがより好ましい。
含フッ素単量体合成工程後の組成物において、式(4)で表される含フッ素単量体を基準とする質量百万分率で表して、式(5)で表される含フッ素単量体の含有量を1500ppm以下とすることにより、後の工程を経て得られる含フッ素重合体において、ロット毎の含フッ素重合体の重量平均分子量のバラつきを小さくすることができる。
以下、各方法について詳述する。
一般的なカラム用筒状基材に、充填剤を詰め、移動相に有機溶剤を用いて、組成物を流すことで組成物中から式(5)で表される含フッ素単量体の除去を行う。
充填剤は、特に限定されず、シリカゲルやアルミナゲルが好ましく、アルミナゲルがより好ましい。充填剤は、1種を用いてもよく、2種以上を用いてもよい。
移動相は、特に限定されず、ヘキサン、ヘプタン、トルエン、酢酸エチル等一般有機溶剤を使用することができる。また、移動相は、1種を用いてもよく、2種以上を用いてもよい。
カラムクロマトグラフを行う際の温度は0℃~40℃の範囲が好ましく、20℃~30℃の範囲であることがより好ましい。
充填剤の添加量(高さ)を増やすと多くの時間が必要になるが、充填剤の添加量(高さ)を増やすことで分離度は向上する。カラム用筒状基材として型番:ILC-B22-300、製造元:桐山製作所を用いる場合は、充填剤の高さは、5cm~15cmが望ましい。
精密蒸留を用いて組成物から式(5)で表される含フッ素単量体を除去する際に必要な蒸留塔の理論段数は、5段以上、40段以下である。
理論段数が5段未満では充分に式(5)で表される含フッ素単量体を除去することは困難である。蒸留塔の段数は高いほど、式(5)で表される含フッ素単量体を分離除去する能力が向上するが、40段を超えると、分離除去する能力が上限に近づき、費用対効果が向上しにくくなる。
また、蒸留塔に酸素を導入してもよい。
式(4)で表される含フッ素単量体100質量部に対して重合禁止剤が0.01質量部未満であると、式(4)で表される含フッ素単量体が重合することを防ぎにくくなる。
式(4)で表される含フッ素単量体100質量部に対して重合禁止剤が5質量部を超えると、式(4)で表される含フッ素単量体の重合を防ぐ効果が上限に近づき、費用対効果が向上しにくくなる。
なお、組成物中の式(4)で表される含フッ素単量体の含有量は、ガスクロマトグラフィーにより測定することができる。
晶析を用いて、組成物から式(5)で表される含フッ素単量体を除去することができる。
晶析は、組成物を、良溶媒に溶解し、貧溶媒を添加したり、温度を下げることで、式(4)で表される含フッ素単量体を析出させ、結晶を成長させる操作である。
ニトリル類としてはアセトニトリル、ベンゾニトリル等が挙げられる。
ケトン類としてはアセトン、メチルエチルケトン、ジエチルケトン、メチル-n-プロピルケトン、メチル-iso-プロピルケトン、メチル-n-ブチルケトン、メチル-iso-ブチルケトン等が挙げられる。
アミド類としては、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N,N-ジメチルイミダゾリジノン等が挙げられる。
スルホキシド類としてはジメチルスルホキシド等が挙げられる。
エーテル類としてはジエチルエーテル、メチル-t-ブチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン等が挙げられる。
ハイドロフルオロカーボン類としては、トリフルオロメタン、ジフルオロメタン、1,1,1,2-テトラフルオロエタン、1,1,1-テトラフルオロエタン、1,1-ジフルオロエタン、1,1,1,2,3,3,3-ヘプタフルオロプロパン、1,1,1,3,3,3-ヘキサフルオロプロパン、1,1,1,3,3-ヘプタフルオロプロパン、1,1,1,3,3-ペンタフルオロブタン、1,1,1,2,2,3,4,5,5,5-デカフルオロペンタン、1,1,2,2,3,3,4-ヘプタフルオロシクロペンタン等が挙げられる。
ハイドロフルオロエーテル類としては、メチル1,1,2,2,2-ペンタフルオロエチルエーテル、メチルトリフルオロメチルエーテル、メチル1,1,2,2-テトラフルオロエチルエーテル、1,1,2,2-テトラフルオロ-1-(2,2,2-トリフルオロエトキシ)エタン、(2,2,3,3-テトラフロオプロピル)(1,1,2,3,3,3-ヘキサフルオロプロピル)エーテル、(メチル)(ノナフルオロブチル)エーテル、(メチル)(ノナフルオロイソブチル)エーテル、(エチル)(ノナフルオロブチル)エーテル、(エチル)(ノナフルオロイソブチル)エーテル、1,1,1,2,2,3,4,5,5,5-デカフルオロ-3-メトキシ-4-(トリフルオロメチル)ペンタン、2-トリフルオロメチルー3-エトキシ-ドデカフルオロヘキサン、1,1,1,2,3-ヘキサフルオロ-4-(1,1,2,3,3,3-ヘキサフルオロプロポキシ)ペンタン等が挙げられる。
炭化水素類としてはブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン等が挙げられる。
芳香族系炭化水素類としてはベンゼン、トルエン、キシレン、メシチレン、パーフルオロベンゼン等が挙げられる。
これら溶媒より選ばれた少なくとも1種の化合物を良溶媒または貧溶媒として用いることが好ましい。
式(4)で表される含フッ素単量体100質量部に対して、溶媒の量が50質量部未満では晶析にて析出した式(4)で表される含フッ素単量体のスラリーの攪拌混合が難しい。
式(4)で表される含フッ素単量体100質量部に対して、溶媒を2000質量部を超えて加え溶解させたとしても、不純物を除去する効率は上限に近づき、費用対効果が向上しにくくなる。
なお、組成物中の式(4)で表される含フッ素単量体の含有量は、ガスクロマトグラフィーにより測定することができる。
次に、本開示の含フッ素重合体の製造方法では、重合工程を行う。
重合工程では、含フッ素単量体精製工程後の組成物を用いて式(4)で表される含フッ素単量体を重合することにより、式(1)で表される繰り返し単位を含む含フッ素重合体とする。
なお、含フッ素単量体精製工程後の組成物には、除去しきれない式(5)で表される含フッ素単量体が含まれるので、この式(5)で表される含フッ素単量体も重合する。そのため、得られる含フッ素重合体は、式(2)で表される繰り返し単位を含むことになる。
そのため、得られる含フッ素重合体は、下記式(8)で表される繰り返し単位を含んでいてもよい。
そのため、得られる含フッ素重合体は、このような繰り返し単位を含んでいてもよい。
すなわち、ヘキサフルオロイソプロパノール基(-C(CF3)2OH)を有する単量体、アクリル酸エステル類、メタクリル酸エステル類、含フッ素アクリル酸エステル類、含フッ素メタクリル酸エステル類、スチレン類、含フッ素スチレン類、ビニルエーテル類、含フッ素ビニルエーテル類、アリルエーテル類、含フッ素アリルエーテル類、不飽和アミド類、オレフィン類、含フッ素オレフィン類、ノルボルネン化合物、含フッ素ノルボルネン化合物、ビニルシラン類、ビニルスルホン酸またはビニルスルホン酸エステルアクリル酸、メタクリル酸マレイン酸、無水マレイン酸、フマル酸、二酸化硫黄等である。
酸分解性基を含む単量体を用いて含フッ素重合体を製造することで、含フッ素重合体をレジストとして用いた際に、基板に成膜したレジスト膜に波長300nm以下の電磁波または電子線等の高エネルギー線の露光により酸分解性基が分解しレジスト膜中で酸が発生する。
この酸により、現像における露光部のレジスト膜のアルカリ現像液への溶解性を向上させることができる。
ラクトン構造を有する単量体を用いて含フッ素共重合体を製造することで、含フッ素重合体をレジストとして用いた際に、含フッ素共重合体を含むレジスト膜と基板との密着性を向上させることができる。また当該含フッ素共重合体を上層膜形成用組成物に用い、レジストパターン上の上層膜とした場合、下層のレジストパターンとの密着性を向上させるばかりでなく、現像する際に現像液との親和性を高めたり、高精細なレジストパターンを得ることが可能となる。
また、これらの化合物は、シクロヘキシル基、ノルボルニル基、芳香環、もしくはその環状構造内に水素やカルボニル結合を有した環状型ビニル類またはアリルエーテル類を構造中に含有してもよく、これらを有する水素原子の一部または全部がフッ素原子で置換されていてもよい。
含フッ素オレフィン類としては、フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、クロロトリフルオロエチレン、テトラフルオロエチレン、ヘキサフルオロプロピレン、ヘキサフルオロイソブテン等を例示することができる。
このような単量体としては、シクロペンタジエン、シクロヘキサジエンと不飽和化合物とのDiels-Alder付加反応で合成されるノルボルネン化合物が挙げられる。
1,1,2,2-テトラヒドロヘプタデカフルオロ-n-デシルアクリレートを加えて得られる含フッ素重合体を上層膜の成分とした場合、上層膜の下層のレジスト膜への密着性が向上するとともに上層膜表面の撥水性が向上するため、水を露光媒体とする液浸露光にて露光時間の短縮が可能になる。また表面張力を低減でき、上層膜表面の平滑化、膜厚の均一化が図れる。
別の単量体由来の繰り返し単位の割合が、1mol%未満であると、含フッ素重合体をレジストとした際に期待される有機溶剤への溶解性が向上する効果、基板にレジスト膜を形成した際のレジスト膜と基板との密着性、レジストパターンの耐エッチング性が向上する効果を得にくくなる。
別の単量体由来の繰り返し単位の割合が、80mol%を超えると、式(1)で表される繰り返し単位の割合が少なくなり、レジスト膜の透明性を向上させる効果、溶剤溶解性を向上させる効果が得られにくくなる。
これらの中では、ラジカル重合反応であることが好ましい。
過酸化物系化合物としては、t-ブチルパーオキシピバレート、ジ-t-ブチルパーオキシド、i-ブチリルパーオキシド、ラウロイルパーオキサイド、スクシン酸パーオキシド、ジシンナミルパーオキシド、ジ-n-プロピルパーオキシジカーボネート、t-ブチルパーオキシアリルモノカーボネート、過酸化ベンゾイル、過酸化水素または過硫酸アンモニウム等が挙げられる。
レドックス系化合物としては、酸化剤と還元剤の組み合わせで用い、酸化剤側として、過酸化水素、過硫酸塩、クメンヒドロペルオキシド等が挙げられ、還元剤側として、鉄(II)イオン塩、銅(I)イオン塩、アンモニア、トリエチルアミン等が挙げられる。
重合溶剤としては、ラジカル重合反応を阻害しないものであれば特に限定されず、有機溶剤であってもよく、水であってもよい。
有機溶剤としては、炭化水素系溶剤、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、エーテル系溶剤、環状エーテル系溶剤、フロン系溶剤、芳香族系溶剤等を上げることができる。
これらの溶剤は1種のみを用いてもよく、2種類以上を併用してもよい。
ケトン系溶剤としては、アセトン、メチルイソブチルケトン等を例示することができる。
炭化水素系溶剤としては、トルエン、シクロヘキサン等を例示することができる。
アルコール系溶剤としては、メタノール、イソプロピルアルコール、エチレングリコールモノメチルエーテルを例示することができる。
ラジカル重合反応における反応温度は、ラジカル重合開始剤あるいはラジカル重合開始剤の種類により適宜変更されるが、20℃以上、200℃以下であることが好ましく、30℃以上、140℃以下であることがより好ましい。
具体的には再沈殿、ろ過、減圧下での加熱留出等の方法を例示することができる。
なお、本明細書において、「得られる含フッ素重合体の重量平均分子量の標準偏差」とは、同じ条件で製造した6ロットの含フッ素重合体の重量平均分子量の標準偏差を意味する。
装置:東ソー社製、HLC-8320GPC
重合性単量体分析用カラム:東ソー社製、TSKgelシリーズ(G2500HXL、G2000HXL、G1000HXL、G1000HXLの順に直列に接続)
重合体分析用カラム:東ソー社製、TSKgelシリーズ(G2500HXL、G2000HXL、G1000HXL、G1000HXLの順に直列に接続)
温度プログラム:40℃(保持)
流速:1mL/分
検出器:示差屈折検出器(RI)
溶離液:テトラヒドロフラン(THF)
基準物質:ポリスチレン標準液
しかし、本開示の含フッ素重合体の製造方法で製造された含フッ素重合体は、ロット毎の含フッ素重合体の重量平均分子量のバラつきが少ない。そのため、本開示で得られる含フッ素重合体を使用する微細なレジストパターンの形成では、現像工程後得られるパターン表面の平滑性が良好となる。
また、得られた含フッ素重合体を用いて形成されたレジスト膜や、レジストパターンは、透明性が高く、溶剤溶解性が高い。
<含フッ素単量体合成工程>
温度計、還流冷却器および攪拌器を備えた1Lの三口フラスコに、1,1,1-トリフルオロ-2-(トリフルオロメチル)ペンタン-1,3-ジオール(下記式(3-1)で表される化合物)100g(0.44mol)、メタクリル酸無水物74.6g(0.48mol)、メタンスルホン酸4.2g(0.044mol)、トルエン400gおよびフェノチアジン0.5gを入れた。その後、三口フラスコの底部を50℃に調温したオイルバスに浸し、攪拌しつつ、4時間反応させ組成物を得た。
組成物をガスクロマトグラフィーにより測定したところ、副反応物であるメタクリル酸を除き、反応液中には、メタクリル酸5,5,5-トリフルオロ-4-ヒドロキシ-4-トリフルオロメチルペンタン-2-イル(式(4-1)で示される化合物)が94.5質量%、1,1,1-トリフルオロ-2-(トリフルオロメチル)ペンタン-1,3-ジオールが1.6質量%、メタクリル酸無水物が2.0質量%、その他の化合物が1.9質量%含まれていることが判明した。
得られた組成物を分液ロートに入れ、重曹水400gを加え2回洗浄した後、有機層を採取し、硫酸マグネシウム30gを加え乾燥した後、硫酸マグネシウムを濾過により除去した。濾液に重合禁止剤としてフェノチアジンを0.7g添加し、溶剤留去をした後、減圧蒸留(8Torr=1.1kPa)を行い、80℃~82℃の留分を集め、留分112gを得た。収率は87%であった。
得られた留分をオールダーショウ式蒸留塔にて精密蒸留し、圧力0.5kPaにて沸点80℃の留分2.76kgを得た。
得られた留分をGC-MSで測定したところ、メタクリル酸5,5,5-トリフルオロ-4-ヒドロキシ-4-トリフルオロメチルペンタン-2-イル(式(4-1)で表される含フッ素単量体)の純度は99.8%であった。
精密蒸留前にGC-MSで測定したメタクリル酸1,1,1-トリフルオロ-2-(トリフルオロメチル)ペンタン-2,4-ジイル(式(5-1)で表される含フッ素単量体)の濃度は2,600ppmであったが、精密蒸留後は10ppmに減少していた。このようにして精密蒸留で純度を高めたメタクリル酸5,5,5-トリフルオロ-4-ヒドロキシ-4-トリフルオロメチルペンタン-2-イル(式(4-1)で表される含フッ素単量体)を含む組成物を得た。この組成物をメタクリル酸5,5,5-トリフルオロ-4-ヒドロキシ-4-トリフルオロメチルペンタン-2-イル(式(4-1)で表される含フッ素単量体)の標準試料とした。
温度計、還流冷却器および攪拌器を備えた1Lの三口フラスコに、メタクリル酸5,5,5-トリフルオロ-4-ヒドロキシ-4-トリフルオロメチルペンタン-2-イル(式(4-1)で表される含フッ素単量体)の標準試料100gを入れ、さらにトリエチルアミン60g、N,N-ジメチルアミノピリジン4gおよびフェノチアジン1gを加えた。フラスコ底部を氷浴に浸け、攪拌しつつ無水メタクリル酸79gを滴下した後、室温に戻して一時間攪拌し反応液を得た。反応液を分液ロートに移し、トルエン300gで希釈後、希塩酸200mLを加え反応を終了させ、有機層を分取した。分取した有機層を水200gで2回洗浄した後にロータリーエバポレーターで溶剤を留去した。次いで、ビグリュー管を備えた蒸留装置にて蒸留を行った。減圧度0.5kPaで86℃~88℃の留分を採取し16gの油分を得た。GC-MSで測定した油分には、メタクリル酸1,1,1-トリフルオロ-2-(トリフルオロメチル)ペンタン-2,4-ジイル(式(5-1)で表される含フッ素単量体)が96質量%、未反応のメタクリル酸5,5,5-トリフルオロ-4-ヒドロキシ-4-トリフルオロメチルペンタン-2-イル(式(4-1)で表される含フッ素単量体)が2.5質量%含まれていた。当該油分を、メタクリル酸1,1,1-トリフルオロ-2-(トリフルオロメチル)ペンタン-2,4-ジイル(式(5-1)で表される含フッ素単量体)の標準試料とした。
作製したメタクリル酸5,5,5-トリフルオロ-4-ヒドロキシ-4-トリフルオロメチルペンタン-2-イル(式(4-1)で表される含フッ素単量体)の標準試料及びメタクリル酸1,1,1-トリフルオロ-2-(トリフルオロメチル)ペンタン-2,4-ジイル(式(5-1)で表される含フッ素単量体)の標準試料を用い、表1に示す割合となるように、原料組成物A~Fを調製した。
<重合工程>
室温(約20℃)にて、原料組成物A、100gを500mLの容器に仕込み、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)(和光純薬工業株式会社製、製品名V-601)6.26gを溶解させた2-ブタノン200gを加え、原料組成物Aの溶液とした後、滴下ロートへ移した。次いで、別途、2-ブタノン100gを仕込んだ500mLの反応器に本滴下ロートを取り付け、2-ブタノンを78℃まで昇温した。
実施例1に係る含フッ素重合体の分子量をゲルパーミエーションクロマトグラフィ(GPC)で測定したところ、重量平均分子量は9575であった(N=1)。
原料組成物Aに換えて原料組成物B~原料組成物Eを使用した以外は、実施例1と同様にして、それぞれ、実施例2~実施例5に係る含フッ素重合体を製造した。そして、実施例2~実施例5に係る含フッ素重合体の重量平均分子量を測定し、含フッ素重合体の重量平均分子量の標準偏差を含フッ素重合体の重量平均分子量の平均値で割った数値である相対標準偏差を算出した。結果を表2に示す。
室温(約20℃)にて、原料組成物A80g、3,5-ビス(1,1,1,3,3,3-ヘキサフルオロ-2-ヒドロキシイソプロピル)シクロヘキシルメタクリレート(式(11)で表される単量体)20gを500mLの容器に仕込み、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)(和光純薬工業株式会社製、製品名V-601)6.26gを溶解させた2-ブタノン200gを加え、原料組成物Aとの混合溶液とした後、滴下ロートへ移した。次いで、別途、2-ブタノン100gを仕込んだ500mLの反応器に本滴下ロートを取り付け、2-ブタノンを78℃まで昇温した。
次に、反応液より、2-ブタノンを除去し、実施例6に係る含フッ素重合体の分子量をGPCで測定したところ、9669であった(N=1)。
原料組成物Aに換えて原料組成物Cを使用した以外は、実施例6と同様にして、実施例7に係る含フッ素重合体を製造した。そして、実施例7に係る含フッ素重合体の重量平均分子量を測定し、含フッ素重合体の重量平均分子量の標準偏差を含フッ素重合体の重量平均分子量の平均値で割った数値である相対標準偏差を算出した。結果を表2に示す。
室温(約20℃)にて、原料組成物A95g、1,1,2,2-テトラヒドロヘプタデカフルオロ-n-デシルアクリレート(式(12)で表される単量体)5gを500mLの容器に仕込み、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)6.26gを溶解させた2-ブタノン200gを加え、原料組成物Aとの混合溶液とした後、滴下ロートへ移した。次いで、別途、2-ブタノン100gを仕込んだ500mLの反応器に本滴下ロートを取り付け、2-ブタノンを78℃まで昇温した。
反応液より、2-ブタノンを除去し得られた実施例8に係る含フッ素共重合体の分子量をゲルパーミエーションクロマトグラフィ(GPC)で測定したところ、重量平均分子量は9532であった(N=1)。
原料組成物Aに換えて原料組成物Cを使用した以外は、実施例8と同様にして、実施例9に係る含フッ素重合体を製造した。そして、実施例9に係る含フッ素重合体の重量平均分子量を測定し、含フッ素重合体の重量平均分子量の標準偏差を含フッ素重合体の重量平均分子量の平均値で割った数値である相対標準偏差を算出した。結果を表2に示す。
原料組成物Aに換えて原料組成物Fを使用した以外は、実施例1と同様にして、比較例1に係る含フッ素重合体を製造した。そして、比較例1に係る含フッ素重合体の重量平均分子量を測定し、含フッ素重合体の重量平均分子量の標準偏差を含フッ素重合体の重量平均分子量の平均値で割った数値である相対標準偏差を算出した。結果を表2に示す。
原料組成物Aに換えて原料組成物Fを使用した以外は、実施例8と同様にして、比較例2に係る含フッ素重合体を製造した。そして、比較例2に係る含フッ素重合体の重量平均分子量を測定し、含フッ素重合体の重量平均分子量の標準偏差を含フッ素重合体の重量平均分子量の平均値で割った数値である相対標準偏差を算出した。結果を表2に示す。
一方、メタクリル酸1,1,1-トリフルオロ-2-(トリフルオロメチル)ペンタン-2,4-ジイル(式(5-1)で表される含フッ素単量体)の濃度が1500ppmを超える原料組成物Fを用いて製造した比較例1及び2に係る含フッ素重合体のRSDの数値は大きな値であった。
Claims (14)
- 下記式(1)で表される繰り返し単位と下記式(2)で表される繰り返し単位とを含む含フッ素重合体の製造方法であって、
下記式(3)で表されるジオールに不飽和カルボン酸、前記不飽和カルボン酸のエステル、前記不飽和カルボン酸の酸ハライド及び前記不飽和カルボン酸の無水物からなる群から選択される少なくとも1種を反応させて、主反応物である下記式(4)で表される含フッ素単量体と、副反応物である下記式(5)で表される含フッ素単量体とを含む組成物を得る含フッ素単量体合成工程と、
前記組成物から前記式(5)で表される含フッ素単量体を除去し、前記式(4)で表される含フッ素単量体を基準とする質量百万分率で表して、前記式(5)で表される含フッ素単量体の含有量を1500ppm以下とする、含フッ素単量体精製工程と、
前記含フッ素単量体精製工程後の前記組成物を用いて重合反応を行い、下記式(1)で表される繰り返し単位と下記式(2)で表される繰り返し単位とを含む含フッ素重合体とする、重合工程とを含むことを特徴とする含フッ素重合体の製造方法。
- 前記重合工程では、得られる前記含フッ素重合体の重量平均分子量の標準偏差を、前記含フッ素重合体の重量平均分子量の平均値で割った数値である相対標準偏差が、0.10~1.10となるように、前記含フッ素重合体を合成する請求項1に記載の含フッ素重合体の製造方法。
- R5がトリフルオロメチル基である、請求項1または2に記載の含フッ素重合体の製造方法。
- R3及びR4が水素原子である、請求項1~3のいずれか1項に記載の含フッ素重合体の製造方法。
- R1がメチル基またはiso-プロピル基であり、R2が水素原子である、請求項1~4のいずれか1項に記載の含フッ素重合体の製造方法。
- 前記重合工程では、前記式(4)で表される含フッ素単量体及び前記式(5)で表される含フッ素単量体以外の別の単量体を含む前記組成物を用いて、重合反応を行う請求項1~5のいずれか1項に記載の含フッ素重合体の製造方法。
- 前記重合工程における重合反応は、ラジカル重合反応である請求項1~6のいずれか1項に記載の含フッ素重合体の製造方法。
- 前記ラジカル重合反応を有機溶剤中で行う請求項7に記載の含フッ素重合体の製造方法。
- R5がトリフルオロメチル基である、請求項9に記載の組成物。
- R3、R4が水素原子である、請求項9または10に記載の組成物。
- R1がメチル基またはiso-プロピル基であり、R2が水素原子である、請求項9~11のいずれか1項に記載の組成物。
- さらに、前記式(4)で表される含フッ素単量体及び前記式(5)で表される含フッ素単量体以外の別の単量体を含む請求項9~12のいずれか1項に記載の組成物。
- さらに有機溶剤を含む請求項9~13のいずれか1項に記載の組成物。
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