WO2011148603A1 - 環状化合物の精製方法 - Google Patents
環状化合物の精製方法 Download PDFInfo
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- WO2011148603A1 WO2011148603A1 PCT/JP2011/002825 JP2011002825W WO2011148603A1 WO 2011148603 A1 WO2011148603 A1 WO 2011148603A1 JP 2011002825 W JP2011002825 W JP 2011002825W WO 2011148603 A1 WO2011148603 A1 WO 2011148603A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
Definitions
- the present invention relates to a purification method for a cyclic compound, and more particularly to an industrially advantageous purification method for a cyclic compound with a reduced metal content.
- a positive resist composition using as a main component a low molecular weight cyclic polyphenol compound having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group Patent Documents 1 to 9
- Patent Documents 1 and 2 Non-Patent Documents 1 and 2
- an alkali development type resist composition see Patent Document 9 and Non-Patent Document 3 using a low molecular weight cyclic polyphenol compound as a main component
- these low molecular weight cyclic polyphenol compounds have a low molecular weight, they are expected to give a resist pattern having a small molecular size, high resolution, and low roughness. Further, the low molecular weight cyclic polyphenol compound has a rigid cyclic structure in its skeleton, and thus provides high heat resistance despite its low molecular weight.
- the metal content of the resist composition is an important performance item for improving the yield. That is, when a resist composition having a high metal content is used, the metal remains in the drawn pattern, and the electrical characteristics of the semiconductor are deteriorated. Therefore, it is required to reduce the metal content. .
- a method for producing a cyclic compound with a reduced metal content a method of bringing a mixture containing a cyclic compound and an organic solvent into contact with an ion exchange resin, a method of filtering with a filter, or the like can be considered.
- an ion exchange resin when various metal ions are contained, it is difficult to select an ion exchange resin, and it is difficult to remove depending on the type of metal, and removal of nonionic metals. There is a problem that it is difficult, and there is a problem that the running cost is high.
- the method of filtering with a filter has a problem that it is difficult to remove the ionic metal. Therefore, establishment of an industrially advantageous purification method for cyclic compounds having a reduced metal content is desired.
- Japanese Patent Laid-Open No. 11-153863 Japanese Patent Laid-Open No. 11-322656 JP 2002-328473 A JP 2003-321423 A JP 2005-170902 A JP 2006-276659 A JP 2006-276742 A JP 2007-8875 A JP 2009-173623 A
- An object of the present invention is to provide an industrially advantageous purification method for a cyclic compound having a reduced metal content.
- the present inventors have found that the content of various metals is significantly reduced by bringing a solution containing a cyclic compound and an organic solvent into contact with water or an acidic aqueous solution.
- the present invention has been reached. That is, the present invention is as follows. 1.
- a method for purifying a cyclic compound with a reduced metal content comprising a step of bringing a solution containing a cyclic compound represented by the following formula (1) and an organic solvent into contact with water or an acidic aqueous solution.
- L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms.
- R 1 is independently an alkyl group having 1 to 20 carbon atoms, C3-C20 cycloalkyl group, C6-C20 aryl group, C1-C20 alkoxyl group, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen atom, carboxyl group, C2-C2 20 acyl groups, C1-C20 alkylsilyl groups, C2-C20 substituted methyl groups, C3-C3 20 1-substituted ethyl groups, 1-substituted n-propyl groups having 4 to 20 carbon atoms, 1-
- a functional group selected from the group consisting of a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen atom, a carboxyl group, and an alkylsilyl group having 1 to 20 carbon atoms, or a substituted methyl group having 2 to 20 carbon atoms, 1-substituted ethyl group having 3 to 20 carbon atoms, 1-substituted n-propyl group having 4 to 20 carbon atoms, 1-branched alkyl group having 3 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms, carbon number Selected from the group consisting of an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group.
- R 5 is hydrogen or an alkyl group having 1 to 10 carbon atoms
- m is an integer of 1 to 4
- p is an integer of 0 to 5.
- the acidic aqueous solution is an aqueous solution of one or more mineral acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. 6).
- the acidic aqueous solution is a group consisting of acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. 5.
- Item 5 The purification method according to any one of Items 1 to 4, wherein the acidic aqueous solution is an aqueous solution of at least one polyvalent carboxylic acid selected from succinic acid, tartaric acid, and citric acid. 8).
- X 2 is a hydrogen atom or a halogen atom
- m 5 is an integer of 0 to 3
- m + m 5 4. is there.
- 12 Item 12.
- Item 12 The purification method according to Item 11, wherein the compound represented by the formula (2) is selected from the group consisting of each compound represented by the following formula (4).
- R 1 , R 4 , p and m are the same as described above, provided that at least one R 1 is an acid-dissociable functional group, and X 2 is a hydrogen atom or a halogen atom.
- the purification method according to item 16 wherein the compound represented by the formula (7) is selected from the group consisting of each compound represented by the following formula (8).
- R 1, R 4, X 2, p are as defined above.
- R 1 is .m 3 is 2 an acid dissociable functional group
- m 4 Is 1.
- Item 18 The purification method according to Item 17, wherein the compound represented by the formula (8) is selected from the group consisting of each compound represented by the following formulas (9-1) and (9-2). (In formulas (9-1) and (9-2), R 1 is as defined above, provided that at least one R 1 is an acid-dissociable functional group.)
- the present invention can provide a method for purifying a cyclic compound in which the contents of various metals are significantly reduced.
- a cyclic compound is dissolved in an organic solvent, and the solution is brought into contact with water or an acidic aqueous solution so that the metal content contained in the solution is transferred to the aqueous phase, thereby reducing the cyclic content of the metal content.
- the cyclic compound used in the present invention is a cyclic compound represented by the following formula (1).
- L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms.
- R 1 is independently an alkyl group having 1 to 20 carbon atoms, C3-C20 cycloalkyl group, C6-C20 aryl group, C1-C20 alkoxyl group, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen atom, carboxyl group, C2-C2
- R 1 is independently an alkyl group having 1 to 20 carbon atoms, C3-C20 cycloalkyl group, C6-C20 aryl group, C1-C20 alkoxyl group, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen atom, carboxyl group, C2-C2
- Preferred examples of the cyclic compound represented by the above formula (1) include the following compounds.
- R 1 , R 4 , p, and m are the same as described above.
- X 2 is a hydrogen atom or a halogen atom
- m 5 is an integer of 0 to 3
- m + m 5 4
- m 3 is 2, and m 4 is 1.
- the cyclic compound When the cyclic compound does not have the acid dissociable functional group in the compound, the cyclic compound becomes a cyclic compound (A) useful as a main component of the negative resist composition, and the acid dissociation property is contained in the compound. When it has one or more functional groups, the cyclic compound becomes a cyclic compound (B) that is useful as a main component of the positive resist composition.
- the cyclic compound (A) is preferably the following.
- the cyclic compound (A) represented by the following formulas (4) and (5) is preferred.
- the cyclic compound (A) is more preferably a compound represented by the following formula (6-1) or (6-2).
- cyclic compound (B) As the cyclic compound (B), the following are preferable.
- the cyclic compound (B) represented by the following formulas (7) and (8) is preferred.
- R 1 , R 4 , p and m are the same as described above, provided that at least one R 1 is an acid-dissociable functional group.
- the cyclic compound (B) is more preferably a compound represented by the following formula (9-1) or (9-2).
- R 1 is as defined above, provided that at least one R 1 is an acid-dissociable functional group.
- the acid-dissociable functional group may be appropriately selected from those proposed for hydroxystyrene-based resins and (meth) acrylic acid-based resins used in chemically amplified resist compositions for KrF and ArF. it can.
- the acid dissociable functional group preferably has no crosslinkable functional group.
- the substituted methyl group is usually a substituted methyl group having 2 to 20 carbon atoms, preferably a substituted methyl group having 4 to 18 carbon atoms, and more preferably a substituted methyl group having 6 to 16 carbon atoms.
- methoxymethyl group, methylthiomethyl group, ethoxymethyl group, n-propoxymethyl group isopropoxymethyl group, n-butoxymethyl group, t-butoxymethyl group, 2-methylpropoxymethyl group, ethylthiomethyl group, methoxy Ethoxymethyl group, phenyloxymethyl group, 1-cyclopentyloxymethyl group, 1-cyclohexyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4-methoxyphenacyl group, piperonyl group, and the following formula ( The substituent etc. which are shown by 11) can be mentioned.
- R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, t -Butyl group, n-butyl group, etc.
- the 1-substituted ethyl group is usually a 1-substituted ethyl group having 3 to 20 carbon atoms, preferably a 1-substituted ethyl group having 5 to 18 carbon atoms, and more preferably a substituted ethyl group having 7 to 16 carbon atoms. .
- R 2 is the same as described above.
- the 1-substituted-n-propyl group is usually a 1-substituted-n-propyl group having 4 to 20 carbon atoms, preferably a 1-substituted-n-propyl group having 6 to 18 carbon atoms, and having 8 carbon atoms. More preferred are 1 to 16 1-substituted-n-propyl groups. Examples thereof include a 1-methoxy-n-propyl group and a 1-ethoxy-n-propyl group.
- the 1-branched alkyl group is usually a 1-branched alkyl group having 3 to 20 carbon atoms, preferably a 1-branched alkyl group having 5 to 18 carbon atoms, and more preferably a branched alkyl group having 7 to 16 carbon atoms.
- isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, 2-methyladamantyl group, 2-ethyladamantyl group, etc. Can be mentioned.
- the silyl group is usually a silyl group having 1 to 20 carbon atoms, preferably a silyl group having 3 to 18 carbon atoms, and more preferably a silyl group having 5 to 16 carbon atoms.
- a silyl group having 1 to 20 carbon atoms preferably a silyl group having 3 to 18 carbon atoms, and more preferably a silyl group having 5 to 16 carbon atoms.
- trimethylsilyl group ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, tri-tert-butylsilyl group and triphenylsilyl Groups and the like.
- the acyl group is usually an acyl group having 2 to 20 carbon atoms, preferably an acyl group having 4 to 18 carbon atoms, and more preferably an acyl group having 6 to 16 carbon atoms.
- Examples include acetyl group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, adamantylcarbonyl group, benzoyl group and naphthoyl group.
- the 1-substituted alkoxymethyl group is usually a 1-substituted alkoxymethyl group having 2 to 20 carbon atoms, preferably a 1-substituted alkoxymethyl group having 4 to 18 carbon atoms, and a 1-substituted alkoxy group having 6 to 16 carbon atoms. More preferred are alkoxymethyl groups. Examples thereof include 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group, 1-adamantylmethoxymethyl group, and the like. .
- the cyclic ether group is usually a cyclic ether group having 2 to 20 carbon atoms, preferably a cyclic ether group having 4 to 18 carbon atoms, and more preferably a cyclic ether group having 6 to 16 carbon atoms.
- Examples thereof include a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 4-methoxytetrahydropyranyl group, and a 4-methoxytetrahydrothiopyranyl group.
- the alkoxycarbonyl group is usually an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonyl group having 6 to 16 carbon atoms.
- a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a tert-butoxycarbonyl group, or an acid dissociable functional group represented by n 0 in the following formula (13) Etc.
- the alkoxycarbonylalkyl group is usually an alkoxycarbonylalkyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonylalkyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonylalkyl group having 6 to 16 carbon atoms.
- a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an isopropoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, or an acid dissociative function represented by n 1 to 4 in the following formula (13) Groups and the like.
- R 2 is as defined above, and n is an integer of 0 to 4.
- a substituted methyl group, a 1-substituted ethyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group are preferred, and a substituted methyl group, 1-substituted An ethyl group, an alkoxycarbonyl group and an alkoxycarbonylalkyl group are more preferred because of their high sensitivity, and further an acid dissociable functional group having a structure selected from a cycloalkane having 3 to 12 carbon atoms, a lactone and an aromatic ring having 6 to 12 carbon atoms. Is more preferable.
- the cycloalkane having 3 to 12 carbon atoms may be monocyclic or polycyclic, but is preferably polycyclic. Specific examples include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane and the like. More specifically, monocycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, Examples include polycycloalkanes such as isobornane, tricyclodecane, and tetracyclodecane.
- adamantane, tricyclodecane, and tetracyclodecane are preferable, and adamantane and tricyclodecane are particularly preferable.
- the cycloalkane having 3 to 12 carbon atoms may have a substituent.
- the lactone include butyrolactone or a cycloalkane group having 3 to 12 carbon atoms having a lactone group.
- the 6 to 12 aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring.
- a benzene ring and a naphthalene ring are preferable, and a naphthalene ring is particularly preferable.
- an acid dissociable functional group selected from the group consisting of each group represented by the following formula (10) is preferable in terms of high resolution.
- R 6 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms
- R 7 is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, cyano A group, a nitro group, a heterocyclic group, a halogen atom, or a carboxyl group
- n 1 is an integer of 0 to 4
- n 2 is an integer of 1 to 5
- n 0 is an integer of 0 to 4.
- the acid-dissociable functional group R 1 is a repeating unit represented by the following formula (14) and the following formula (15) or R 1 (R 1 is the same as above) as long as the effects of the present invention are not impaired.
- the substituent which consists of a terminal group shown by these may be sufficient.
- R 1 is the same as described above.
- L is as defined above, and preferably a single bond, a methylene group, an ethylene group or a carbonyl group.
- a plurality of Q may be the same or different.
- n 5 is an integer of 0 to 4
- n 6 is an integer of 1 to 3
- x is an integer of 0 to 3, which satisfies 1 ⁇ n 5 + n 6 ⁇ 5.
- a plurality of n 5 , n 6 and x may be the same or different.
- R 3 is a halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloyloxy group, aryloyloxy group, cyano group, And a substituent selected from the group consisting of nitro groups.
- halogen atom examples include a chlorine atom, a bromine atom, and an iodine atom
- alkyl group examples include a methyl group, an ethyl group, a propyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- Examples thereof include alkyl groups having 1 to 4 carbon atoms such as butyl group; examples of cycloalkyl groups include cyclohexyl group, norbornyl group, adamantyl group, etc .; examples of aryl groups include phenyl group, tolyl group, xylyl group, and naphthyl group.
- Aralkyl groups include benzyl group, hydroxybenzyl group, dihydroxybenzyl group, etc .; alkoxy groups include methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group, an alkoxy group having 1 to 4 carbon atoms such as an ert-butoxy group; an aryloxy group such as a phenoxy group; an alkenyl group such as a vinyl group, a propenyl group, an allyl group, and a butenyl group.
- acyl group examples include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, isovaleryl group, pivaloyl group, and the like.
- Aromatic acyl groups such as benzoyl group and toluoyl group are exemplified; as alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec- Butoxycarbonyl group, tert-butoxycarbonyl
- alkoxycarbonyl group having 2 to 5 carbon atoms such as a group; examples of the alkyloyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, and a pivaloyloxy group.
- the aryloyloxy group includes a benzoyloxy group and the like.
- a plurality of R 3 may be the same or different.
- the acid dissociable functional group means a characteristic group that is cleaved in the presence of an acid to generate an alkali-soluble group.
- the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group.
- a phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable.
- the acid-dissociable functional group preferably has a property of causing a chain-breaking reaction in the presence of an acid in order to enable pattern formation with higher sensitivity and higher resolution.
- cyclic compounds may be used alone or in combination of two or more.
- the cyclic compound may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers and the like.
- the organic solvent used in the present invention is not particularly limited as long as it is an organic solvent that is not arbitrarily miscible with water, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable.
- the amount of the organic solvent used is usually about 1 to 100 times by weight based on the polymer used.
- solvent used examples include ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone and cyclopentanone.
- ethers such as diethyl ether and diisopropyl ether
- esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone and cyclopentanone.
- Ketones such as 2-heptanone and 2-pentanone, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, glycol ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, n-hexane, n -Aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and chloroform, etc. And the like.
- toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, ethyl acetate and the like are preferable, and cyclohexanone is particularly preferable.
- These solvents can be used alone or in combination of two or more.
- the liquid used for contact with the solution containing the cyclic compound and the organic solvent is water or an acidic aqueous solution.
- the acidic aqueous solution used in the present invention is appropriately selected from aqueous solutions in which generally known organic and inorganic compounds are dissolved in water.
- aqueous solution in which an organic acid such as acid, phenolsulfonic acid, p-toluenesulfonic acid or trifluoroacetic acid is dissolved in water may be mentioned.
- aqueous solutions of carboxylic acids such as sulfuric acid, succinic acid, tartaric acid, and citric acid are preferable, aqueous solutions of succinic acid, tartaric acid, and citric acid are preferable, and aqueous solutions of succinic acid are particularly preferable.
- polyvalent carboxylic acids such as succinic acid, tartaric acid, and citric acid are coordinated to metal ions to produce a chelate effect, it is considered that the metal can be removed more.
- the water used here is preferably one having a low metal content, such as ion-exchanged water, for the purpose of the present invention.
- the pH of the acidic aqueous solution used in the present invention is not particularly limited, but if the acidity of the aqueous solution becomes too large, it may adversely affect the cyclic compound, which is not preferable.
- the pH range is about 0 to 5, more preferably about pH 0 to 3.
- the amount of the acidic aqueous solution used in the present invention is not particularly limited, but if the amount is too small, it is necessary to increase the number of extractions for removing the metal, and conversely if the amount of the aqueous solution is too large, May increase operational problems.
- the amount of the aqueous solution used is usually 10 to 200 parts by mass, preferably 20 to 100 parts by mass with respect to 100 parts by mass of the cyclic compound solution dissolved in the organic solvent.
- the extraction treatment is performed by bringing a solution containing the cyclic compound and the organic solvent into contact with water or the acidic aqueous solution.
- the temperature during the extraction treatment is usually 20 to 90 ° C., preferably 30 to 80 ° C.
- the metal content contained in the solution containing the cyclic compound and the organic solvent is transferred to the aqueous phase by mixing well by stirring or the like.
- the standing time is not particularly limited. However, if the standing time is too short, separation between the solution phase containing the cyclic compound and the organic solvent and the aqueous phase is unfavorable. Usually, the standing time is 10 minutes or longer, preferably 30 minutes or longer.
- the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times.
- the solution containing the cyclic compound and the organic solvent extracted and recovered from the aqueous solution after the extraction treatment is further extracted with water. It is preferable to carry out.
- the water used here is preferably one having a low metal content, such as ion-exchanged water, for the purpose of the present invention.
- This extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times.
- the use ratio of both in the extraction process, conditions such as temperature and time are not particularly limited, but may be the same as in the case of the contact process with the acidic aqueous solution.
- the water mixed in the solution containing the cyclic compound and the organic solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Moreover, an organic solvent can be added as needed and the density
- the method for obtaining only the cyclic compound from the obtained solution containing the cyclic compound and the organic solvent can be performed by a known method such as separation under reduced pressure, separation by reprecipitation, or a combination thereof.
- the chemical shift value ( ⁇ ppm, TMS standard) of 1 H-NMR in deuterated dimethyl sulfoxide solvent is 1.2 to 1.4 (m, 20H), 1.7 to 1.9 (m, 20H), 2 .2 to 2.4 (m, 4H) 5.5, 5.6 (d, 4H), 6.0 to 6.8 (m, 24H), 8.4 to 8.5 (m, 8H) there were.
- Example 1 Production of cyclic compound with reduced metal content (Example 1) A 1000 mL four-necked flask (bottomed) was charged with 650 g of a solution of CR-1 dissolved in cyclohexanone (1.7 wt%), and heated to 75 ° C. with stirring. Next, 130 g of an aqueous oxalic acid solution (pH 0.9) was added, and the mixture was stirred for 3 minutes and allowed to stand for 1 hour. Since it separated into the oil phase and the water phase by this, the water phase was removed. The obtained oil phase was charged with 130 g of ultrapure water, stirred for 3 minutes, and allowed to stand for 1 hour to remove the aqueous phase. By repeating this operation four times, a cyclohexanone solution of a cyclic compound was obtained.
- a aqueous oxalic acid solution pH 0.9
- Example 2 A cyclohexanone solution of a cyclic compound was obtained in the same manner as in Example 1, except that 130 g of an aqueous citric acid solution (pH 0.9) was charged instead of 130 g of an aqueous citric acid solution (pH 1.8).
- Example 3 A cyclohexanone solution of a cyclic compound was obtained in the same manner as in Example 1 except that 130 g of tartaric acid aqueous solution (pH 1.8) was charged instead of 130 g of aqueous oxalic acid solution (pH 0.9).
- Example 4 A cyclohexanone solution of a cyclic compound was obtained in the same manner as in Example 1, except that 130 g of an aqueous acetic acid solution (pH 0.9) was charged instead of 130 g of an aqueous acetic acid solution (pH 0.9).
- Example 5 A cyclohexanone solution of a cyclic compound was obtained in the same manner as in Example 1, except that 130 g of ion-exchanged water was added instead of 130 g of the oxalic acid aqueous solution (pH 0.9).
- ⁇ Comparative Example> Production of cyclic compound with reduced metal content by ion exchange resin (Comparative Example 1) After 25 g of ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) was swollen with cyclohexanone, it was packed in a Teflon (registered trademark) column, and the solvent was replaced by passing 500 mL of 1,3-dioxolane. Subsequently, a cyclic compound was obtained by passing 500 g of a solution (1.7 wt%) in which CR-1 was dissolved in 1,3-dioxolane.
- ion exchange resin Mitsubishi Chemical Diaion: SMT100-mix resin
- the present invention can industrially advantageously purify cyclic compounds having a reduced metal content.
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Abstract
Description
すなわち、本発明はつぎの通りである。
1. 下記式(1)で示される環状化合物及び有機溶媒を含む溶液と、水又は酸性の水溶液とを接触させる工程を含むことを特徴とする金属含有量の低減された環状化合物の精製方法。
で表わされる基であり、R4は独立して、炭素数1~20のアルキル基、炭素数3~20のシクロアルキル基、炭素数6~20のアリール基、炭素数1~20のアルコキシ基、シアノ基、ニトロ基、水酸基、複素環基、ハロゲン原子、カルボキシル基、及び炭素数1~20のアルキルシリル基からなる群から選択される官能基、又は炭素数2~20の置換メチル基、炭素数3~20の1-置換エチル基、炭素数4~20の1-置換-n-プロピル基、炭素数3~20の1-分岐アルキル基、炭素数1~20のシリル基、炭素数2~20のアシル基、炭素数2~20の1-置換アルコキシアルキル基、炭素数2~20の環状エーテル基、炭素数2~20のアルコキシカルボニル基及びアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基であり、R5は水素又は炭素数1~10のアルキル基であり、mは1~4の整数であり、pは0~5の整数である。)
2. 前記環状化合物の抽出処理を行う工程をさらに含む第1項に記載の精製方法。
3. 前記抽出処理後、前記環状化合物及び前記有機溶媒を含む溶液相と、水相とに分離する工程をさらに含む第2項に記載の精製方法。
4. 前記環状化合物及び有機溶媒を含む溶液を回収する工程をさらに含む第3項に記載の精製方法。
5. 前記酸性の水溶液が、塩酸、硫酸、硝酸及びリン酸からなる群より選ばれる1種以上の鉱酸の水溶液である第1項~第4項のいずれかに記載の精製方法。
6. 前記酸性の水溶液が、酢酸、プロピオン酸、蓚酸、マロン酸、コハク酸、フマル酸、マレイン酸、酒石酸、クエン酸、メタンスルホン酸、フェノールスルホン酸、p-トルエンスルホン酸及びトリフルオロ酢酸からなる群より選ばれる1種以上の有機酸の水溶液である第1項~第4項のいずれかに記載の精製方法。
7. 前記酸性の水溶液が、蓚酸、酒石酸及びクエン酸から選ばれる少なくとも1種の多価カルボン酸の水溶液である第1項~第4項のいずれかに記載の精製方法。
8. 前記酸性の水溶液が、蓚酸の水溶液である第6項に記載の精製方法。
9. 前記有機溶媒が、トルエン、2-ヘプタノン、シクロヘキサノン、シクロペンタノン、メチルイソブチルケトン、又は酢酸エチルである第1項~第8項のいずれかに記載の精製方法。
10. 前記有機溶媒が、シクロヘキサノンである第9項に記載の精製方法。
11. 前記式(1)で示される環状化合物が下記式(2)で示される各化合物からなる群から選ばれる第1項~第10項のいずれかに記載の精製方法。
12. 前記式(2)で示される化合物が下記式(3)で示される各化合物からなる群から選ばれる第11項に記載の精製方法。
13. 前記式(2)で示される化合物が下記式(4)で示される各化合物からなる群から選ばれる第11項に記載の精製方法。
14. 前記式(4)で示される化合物が下記式(5)で示される各化合物からなる群から選ばれる第13項に記載の精製方法。
15. 前記式(5)で示される化合物が下記式(6-1)及び(6-2)で示される各化合物からなる群から選ばれる第14項に記載の精製方法。
17. 前記式(7)で示される化合物が下記式(8)で示される各化合物からなる群から選ばれる第16項に記載の精製方法。
18. 前記式(8)で示される化合物が下記式(9-1)及び(9-2)で示される各化合物からなる群から選ばれる第17項に記載の精製方法。
本発明は、環状化合物を有機溶媒に溶解させ、その溶液を水又は酸性水溶液と接触させることにより、該溶液に含まれていた金属分を水相に移行させ、金属含有量の低減された環状化合物を精製する方法である。
で表わされる基であり、R4は独立して、炭素数1~20のアルキル基、炭素数3~20のシクロアルキル基、炭素数6~20のアリール基、炭素数1~20のアルコキシ基、シアノ基、ニトロ基、水酸基、複素環基、ハロゲン原子、カルボキシル基、及び炭素数1~20のアルキルシリル基からなる群から選択される官能基、又は炭素数2~20の置換メチル基、炭素数3~20の1-置換エチル基、炭素数4~20の1-置換-n-プロピル基、炭素数3~20の1-分岐アルキル基、炭素数1~20のシリル基、炭素数2~20のアシル基、炭素数2~20の1-置換アルコキシアルキル基、炭素数2~20の環状エーテル基、炭素数2~20のアルコキシカルボニル基及びアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基であり、R5は水素原子又は炭素数1~10のアルキル基であり、mは1~4の整数であり、pは0~5の整数である。)
下記式(4)及び(5)で示される環状化合物(A)が好ましい。
下記式(7)及び(8)で示される環状化合物(B)が好ましい。
また、抽出処理は1回だけでもかまわないが、混合、静置、分離という操作を複数回繰り返して行うのも有効である。
十分乾燥し、窒素置換した滴下漏斗、ジム・ロート冷却管、温度計、攪拌翼を設置した四つ口フラスコ(1000mL)に、窒素気流下で、関東化学社製レゾルシノール(22g、0.2mol)と、4-シクロヘキシルベンズアルデヒド(46.0g,0.2mol)と、脱水エタノール(200mL)を投入し、エタノール溶液を調製した。この溶液を攪拌しながらマントルヒーターで85℃まで加熱した。次いで濃塩酸(35%)75mLを、滴下漏斗により30分かけて滴下した後、引き続き85℃で3時間攪拌した。反応終了後、放冷し、室温に到達させた後、氷浴で冷却した。1時間静置後、淡黄色の目的粗結晶が生成し、これを濾別した。粗結晶をメタノール500mlで2回洗浄し、濾別、真空乾燥させることにより、目的生成物(以下、CR-1と示す)(50g、収率91%)を得た。
この化合物の構造は、LC-MSで分析した結果、目的物の分子量1121を示した。また重ジメチルスルホキシド溶媒中での1H-NMRのケミカルシフト値(δppm,TMS基準)は1.2~1.4(m,20H)、1.7~1.9(m,20H)、2.2~2.4(m,4H)5.5、5.6(d,4H)、6.0~6.8(m,24H)、8.4~8.5(m,8H)であった。
(実施例1)
1000mL容量の四つ口フラスコ(底抜き型)に、CR-1をシクロヘキサノンに溶解させた溶液(1.7wt%)を650g仕込み、攪拌しながら75℃まで加熱した。次いで、蓚酸水溶液(pH 0.9)130gを加え、3分間攪拌後、1時間静置した。これにより油相と水相に分離したので、水相を除去した。得られた油相に、超純水130gを仕込み、3分間攪拌後、1時間静置し、水相を除去した。この操作を4回繰り返すことにより、環状化合物のシクロヘキサノン溶液を得た。
実施例1における蓚酸水溶液(pH 0.9)130gを仕込む代わりに、クエン酸水溶液(pH 1.8)130gを仕込んだこと以外は同様に処理して環状化合物のシクロヘキサノン溶液を得た。
実施例1における蓚酸水溶液(pH 0.9)130gを仕込む代わりに、酒石酸水溶液(pH 1.8)130gを仕込んだこと以外は同様に処理して環状化合物のシクロヘキサノン溶液を得た。
実施例1における蓚酸水溶液(pH 0.9)130gを仕込む代わりに、酢酸水溶液(pH 2.8)130gを仕込んだこと以外は同様に処理して環状化合物のシクロヘキサノン溶液を得た。
実施例1における蓚酸水溶液(pH 0.9)130gを仕込む代わりに、イオン交換水130gを仕込んだこと以外は同様に処理して環状化合物のシクロヘキサノン溶液を得た。
(比較例1)
イオン交換樹脂(三菱化学ダイヤイオン:SMT100-ミックス樹脂)25gをシクロヘキサノンで膨潤後、テフロン(登録商標)カラムに充填し、1,3-ジオキソランを500mL通液することで溶媒置換した。次いでCR-1を1,3-ジオキソランに溶解させた溶液(1.7wt%)500gを通液することで環状化合物を得た。
Claims (18)
- 下記式(1)で示される環状化合物及び有機溶媒を含む溶液と、水又は酸性の水溶液とを接触させる工程を含むことを特徴とする環状化合物の精製方法。
で表わされる基であり、R4は独立して、炭素数1~20のアルキル基、炭素数3~20のシクロアルキル基、炭素数6~20のアリール基、炭素数1~20のアルコキシ基、シアノ基、ニトロ基、水酸基、複素環基、ハロゲン原子、カルボキシル基、及び炭素数1~20のアルキルシリル基からなる群から選択される官能基、又は炭素数2~20の置換メチル基、炭素数3~20の1-置換エチル基、炭素数4~20の1-置換-n-プロピル基、炭素数3~20の1-分岐アルキル基、炭素数1~20のシリル基、炭素数2~20のアシル基、炭素数2~20の1-置換アルコキシアルキル基、炭素数2~20の環状エーテル基、炭素数2~20のアルコキシカルボニル基及びアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基であり、R5は水素原子又は炭素数1~10のアルキル基であり、mは1~4の整数であり、pは0~5の整数である。) - 前記環状化合物の抽出処理を行う工程をさらに含む請求項1に記載の精製方法。
- 前記抽出処理後、前記環状化合物及び前記有機溶媒を含む溶液相と、水相とに分離する工程をさらに含む請求項2に記載の精製方法。
- 前記環状化合物及び有機溶媒を含む溶液を回収する工程をさらに含む請求項3に記載の精製方法。
- 前記酸性の水溶液が、塩酸、硫酸、硝酸及びリン酸からなる群より選ばれる1種以上の鉱酸の水溶液である請求項1~4のいずれかに記載の精製方法。
- 前記酸性の水溶液が、酢酸、プロピオン酸、蓚酸、マロン酸、コハク酸、フマル酸、マレイン酸、酒石酸、クエン酸、メタンスルホン酸、フェノールスルホン酸、p-トルエンスルホン酸及びトリフルオロ酢酸からなる群より選ばれる1種以上の有機酸の水溶液である請求項1~4のいずれかに記載の精製方法。
- 前記酸性の水溶液が、蓚酸、酒石酸及びクエン酸から選ばれる少なくとも1種の多価カルボン酸の水溶液である請求項6に記載の精製方法。
- 前記酸性の水溶液が、蓚酸の水溶液である請求項7に記載の精製方法。
- 前記有機溶媒が、トルエン、2-ヘプタノン、シクロヘキサノン、シクロペンタノン、メチルイソブチルケトン、又は酢酸エチルである請求項1~8のいずれかに記載の精製方法。
- 前記有機溶媒が、シクロヘキサノンである請求項9に記載の精製方法。
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EP2505576B1 (en) * | 2009-11-27 | 2019-04-24 | Mitsubishi Gas Chemical Company, Inc. | Cyclic compound, process for production thereof, radiation-sensitive composition, and resist pattern formation method |
-
2011
- 2011-05-20 CN CN2011800257528A patent/CN102971281A/zh active Pending
- 2011-05-20 JP JP2012517127A patent/JP5725021B2/ja active Active
- 2011-05-20 US US13/700,002 patent/US20130150627A1/en not_active Abandoned
- 2011-05-20 KR KR1020127033217A patent/KR20130124166A/ko not_active Application Discontinuation
- 2011-05-20 EP EP11786306.8A patent/EP2578562A4/en not_active Withdrawn
- 2011-05-20 WO PCT/JP2011/002825 patent/WO2011148603A1/ja active Application Filing
- 2011-05-24 TW TW100118124A patent/TW201204450A/zh unknown
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2016190044A1 (ja) * | 2015-05-27 | 2016-12-01 | 三菱瓦斯化学株式会社 | ヒドロキシ置換芳香族化合物の製造方法 |
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JP7138853B2 (ja) | 2015-05-27 | 2022-09-20 | 三菱瓦斯化学株式会社 | ヒドロキシ置換芳香族化合物の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2578562A1 (en) | 2013-04-10 |
JPWO2011148603A1 (ja) | 2013-07-25 |
EP2578562A4 (en) | 2015-12-02 |
JP5725021B2 (ja) | 2015-05-27 |
US20130150627A1 (en) | 2013-06-13 |
TW201204450A (en) | 2012-02-01 |
KR20130124166A (ko) | 2013-11-13 |
CN102971281A (zh) | 2013-03-13 |
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