• 专利附录
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  • 权利要求
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    • 专利摘要:
    An object of the present invention is to provide a method for purifying an alkoxysilicon compound in which a to-be-purified alkoxysilicon compound containing a metal impurity is treated with a chelate resin having a functional group containing a sulfur atom and a nitrogen atom, thereby reducing the amount of the metal impurity while reducing the amount of the to-be-purified alkoxysilicon compound adsorbed onto the chelate resin, and to provide an alkoxysilicon compound. MEANS OF SOLVING THE PROBLEM The to-be-purified alkoxysilicon compound is treated with a chelate resin having a functional group of any of the following Formulae (1-1) to (1-3): (in Formulae (1-1) to (1-3), * is an end bonding to a resin serving as a carrier).
    公开号:FI20205290A1
    申请号:FI20205290
    申请日:2020-03-24
    公开日:2020-09-29
    发明作者:Shun Kubodera；Hiroaki Yaguchi；Gun Son
    申请人:Nissan Chemical Corp；
    IPC主号:
    专利说明:

    [0001] [0001] — The present invention relates to an industrially useful method for purifying an alkoxysilicon compound to reduce the amount of a metal impurity that causes flaws in a lithography process for the production of a semiconductor device.BACKGROUND ART
    [0002] [0002] — A coating film-forming composition for lithography used in a lithography process for the production of a semiconductor device is reguired to contain a reduced amount of a metal impurity that causes minute flaws (e.g., about 1 to 100 nm, also called "defects, etc.") on a wafer.
    [0003] [0003] Non-Patent Document 1: Jikken Kagaku Koza (Courses in Experimental Chemistry) Vol. 2, p. 114
    [0004] [0004] — An object of the present invention for solving the aforementioned problems is to provide a method for purifying an alkoxysilicon compound in which a to-be- purified alkoxysilicon compound containing a metal impurity is treated with a chelate resin having a functional group containing a specific atom, thereby reducing the amount of the metal impurity while reducing the amount of the to-be-purified alkoxysilicon compound adsorbed onto the chelate resin, and to provide an alkoxysilicon compound.
    [0005] [0005] The present inventors have conducted extensive studies for achieving the aforementioned object, and as a result have found that a method involving treatment of a to-be-purified alkoxysilicon compound containing a metal impurity with a chelate resin — having a functional group containing a sulfur atom and a nitrogen atom can efficiently reduce the amount of the metal impurity while suppressing adsorption of the to-be-purified S alkoxysilicon compound onto the chelate resin. The present invention has been g accomplished on the basis of this finding. N Accordingly, the present invention provides a method for purifying an alkoxysilicon = 25 compound, and an alkoxysilicon compound, which are described below. & 1. A method for purifying an alkoxysilicon compound, the method being S characterized by comprising treating a to-be-purified alkoxysilicon compound containing a N metal impurity with a chelate resin having a functional group containing a sulfur atom and a nitrogen atom.
    [0006] [0006] The method for purifying an alkoxysilicon compound of the present invention can economically and efficiently reduce the amount of a metal impurity regardless of the properties of a to-be-purified alkoxysilicon compound. The present invention can prepare an alkoxysilicon compound wherein the amount of a metal impurity is economically and efficiently reduced regardless of the properties of a — to-be-purified alkoxysilicon compound.OO MODES FOR CARRYING OUT THE INVENTION
    [0008] [0008] — The carrier used in the chelate resin may be silica or a silica component- containing substance. The silica or the silica component-containing substance may be a synthetic or natural product. Preferably, the carrier does not elute impurities. For 5 example, the carrier may be synthetic quartz (SiO2) produced by molding and baking of silica prepared through hydrolysis of a high-purity alkoxysilane. The silica component- containing substance may be, for example, forsterite (2MgO-SiO»), zircon (ZrO, S10), mullite (3A1,03-2S10>), steatite (MgO-Si0»), or cordierite (2MgO-2A1,03-58S10>).
    [0009] [0009] — When the silica or the silica component-containing substance is modified — with the chelating functional group, a silane coupling agent having a functional group capable of reacting with the end of the chelating functional group can be reacted with a silica component on the surfaces of particles of the silica or the silica component- containing substance, to thereby modify the particle surfaces and to introduce the chelating functional group. Examples of the functional group capable of reacting with the end of — the chelating functional group include a vinyl group, an aryl group, a hydroxy group, a halogen group, an epoxy group, and a thiol group. The silane coupling agent may have one to three hydrolyzable groups. The silane coupling agent may have three hydrolyzable groups in view of adhesion to the carrier. The chelate resin prepared by bonding of the chelating functional group to silica particles can be charged into a column and used without — any additional treatment.
    [0010] [0010] — When polystyrene is modified with the chelating functional group, a S chloromethyl group can be introduced to the surfaces of polystyrene particles by using a g chloromethylation agent (e.g., chloromethyl methyl ether), and the chloromethyl group can N be further reacted with the chelating functional group, to thereby introduce the chelating = 25 — functional group to the polystyrene. The polystyrene can be charged in the form of & particles into a column and used. S [0011] — When the carrier used in the chelate resin is polystyrene, the polystyrene N may be crosslinked porous polystyrene prepared by high degree crosslinking for preventing elution of impurities. The crosslinking agent used may be a divinyl compound, such as divinylbenzene or divinylmethane. Polystyrene having a large specific surface area is preferably used as an adsorbent, and porous polystyrene may be used. Porous polystyrene can be prepared by polymerization of styrene with addition of a small amount of a non- solvent.
    [0012] [0012] The aforementioned carrier may be used in the form of particles. When polystyrene or crosslinked porous polystyrene is used in the form of particles, the particle diameter may be, for example, 1 um to 10 mm, or 1 um to 1 mm, or about 10 um to 1 mm. When silica or a silica component-containing substance is used in the form of particles, the particle diameter may be, for example, 1 um to 1 mm, or 1 um to 500 um, or about 10 um to 100 um.
    [0013] [0013] — The chelate resin used in the present invention is characterized by having a functional group containing a sulfur atom and a nitrogen atom. Specific examples of the chelating functional group having a sulfur atom and a nitrogen atom include groups of the following Formulae (1-1) to (1-3): NH NH ON Ks "Sy sn (1-1) (1-2) (1-3) (in Formulae (1-1) to (1-3), * is an end bonding to a resin serving as a carrier). S [0014] — No particular limitation is imposed on the chelate resin, so long as it has g 20 such a functional group. The chelate resin may be a commercially available product. N [0015] — The chelate resin used in the present invention generally exhibits metal E: adsorbability described below. & The chelate resin having the functional group of Formula (1-1) can effectively trap S metals such as Ag, Pt, Cu, Fe, Os, Pd, Rh, Sc, and Sn, ions of these metals, colloids of N 25 hydroxides of these metals, and colloids of oxides of these metals. In particular, the chelate resin can effectively trap platinum or palladium ions contained in an organic solvent. The amount of the functional group contained in the chelate resin may be about
    [0016] [0016] The chelate resin having the functional group of Formula (1-2) or (1-3) can trap many metals under various conditions. The chelate resin can effectively trap metals such as Ca, Cd, Cr, Cs, Cu, Fe, Ir, La, Mg, Os, Pd, Pt, Rh, Ru, Sc, Sn, and Zn, ions of these metals, colloids of hydroxides of these metals, and colloids of oxides of these metals. In particular, the chelate resin is optimal for trapping of Sn and Pt, ions of these metals, colloids of hydroxides of these metals, and colloids of oxides of these metals. The amount of the functional group contained in the chelate resin may be about 0.1 mmol to 5 mmol relative to 1 g of the chelate resin. The chelate resin having the functional group of Formula (1-2) is available as S920 (trade name) from Purolite. The chelate resin having — the functional group of Formula (1-3) is available as Muromac XMS-5418 (trade name) from MUROMACHI CHEMICALS INC.
    [0017] [0017] For removal of a metal impurity with the chelate resin, a solution prepared by redissolution of an oily or solid to-be-purified alkoxysilicon compound in an organic solvent, or a to-be-purified alkoxysilicon-containing solution prepared by synthesis and post-treatment of a to-be-purified alkoxysilicon compound is treated with the chelate resin by the contact catalysis method or the fixed-bed method.
    [0019] [0019] Although the treatment is generally performed once, the treatment may be performed a plurality of times, for example, 2 to 100 times. The treatment period
    [0020] [0020] The amount of the chelate resin used in the present invention may vary depending on the type of a to-be-purified alkoxysilicon compound or the type of an organic solvent used. The amount of the chelate resin is about 0.01 to 1,000% by mass, preferably 0.1 to 500% by mass, more preferably 1% by mass to 100% by mass, relative to the amount of the to-be-purified alkoxysilicon compound.
    [0021] [0021] — In the present invention, a single chelate resin may be used alone, or a mixture of two or more chelate resins may be used. In the present invention, a mixture of any of the chelate resins described hereinabove and an additional chelate resin may be used.
    [0022] [0022] The treatment with the chelate resin may be performed once or a plurality of times. In the latter case, a to-be-purified alkoxysilicon compound containing a metal impurity may be treated one by one or simultaneously with two or more selected from the group consisting of any of the chelate resins described hereinabove, a mixture containing any of the chelate resins described hereinabove, an additional chelate resin, and a mixture of any of the chelate resins described hereinabove and the additional chelate resin.
    [0023] [0023] <To-Be-Purified Alkoxysilicon Compound> The to-be-purified alkoxysilicon compound used in the present invention may be a commercially available compound or a compound synthesized by any known method. In S either case, the metal impurity contained in the compound can be efficiently removed or g reduced. Specific examples of the commercially available to-be-purified alkoxysilicon N compound include compounds of the following Formulae (2-1) to (2-28) available from E 25 — Shin-Etsu Chemical Co., Ltd. > 2S
    [0024] [0024] — The to-be-purified alkoxysilicon compound can be synthesized by a known method (e.g., WO 2011/102470, WO 2019/003767, or Japanese Unexamined Patent
    [0025] [0025] <Organic Solvent> Examples of the solvent used for treatment of the to-be-purified alkoxysilicon compound with the chelate resin in the present invention include, but are not limited to, organic solvents described below.
    [0026] [0026] Examples of the organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, cyclopentyl methyl ether, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2- hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3- methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3- ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, y-butyrolactone, N- methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, n-heptane, hexane, isopropyl ether, diisobutyl ether, diisoamyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 2,5-dimethyltetrahydrofuran. These solvents may be used alone or in combination of two or more species.
    [0027] [0027] — Among these solvents, preferred are, for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, S cyclohexanone, n-heptane, hexane, toluene, isopropyl ether, diisobutyl ether, diisoamyl g ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2- N methyltetrahydrofuran, and 2,5-dimethyltetrahydrofuran. Particularly preferred are = 25 propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol & monomethyl ether acetate, toluene, and isopropyl ether.
    [0029] [0029] <GC Analysis Conditions> The amount of adsorption described below in Examples was measured by GC under the following measurement conditions. Apparatus: GC-2010 Plus, available from SHIMADZU CORPORATION Column: DB-1 Dimethylpolysiloxane, 0.25 um, 0.25 mm x 30 m (Agilent Technologies, Inc.) Inlet temperature: 250°C Split ratio: 100 Column temperature: 100°C (for 15 minutes), temperature rising (15*C/minute), 250°C (for five minutes), temperature rising (15°C/minute), 300°C (for five minutes) Linear velocity: 32.0 cm/sec Detector temperature: 300°C (FID) Analysis time: 38.33 minute Injection amount: 1.0 uL Diluent solvent: propylene glycol monomethyl ether (PGME), cyclopentyl methyl ether (CPME), or acetonitrile
    [0030] [0030] <Synthesis of To-Be-Purified Alkoxysilicon Compound (A)> S [Synthesis Example 1] g A 500-mL four-necked flask was charged with 30.09 g of monoallyl isocyanurate N (available from SHIKOKU CHEMICALS CORPORATION), 150.73 g of toluene, and = 25 171g of Karstedt catalyst [solution of platinum(0)-1,3-divinyl-1,1,3,3- & tetramethyldisiloxane complex (up to 2% by mass as platinum) in xylene] (available from S SIGMA-ALDRICF), and the mixture was stirred at 25*C. Thereafter, 37.78 g of N triethoxysilane (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the mixture in the flask so that the temperature of the mixture was controlled to 30*C or lower. After completion of the dropwise addition, the mixture was heated to 100°C, and reaction was allowed to proceed for 25 hours. After completion of the reaction, toluene and excess triethoxysilane were removed from the resultant reaction mixture with an evaporator. To the resultant crude product was added 303.70 g of dichloromethane, and the mixture was subjected to phase separation three times with 155.14 g of ion-exchange water, to thereby extract an organic phase. Dichloromethane was removed from the organic phase with an evaporator, and 330.86 g of tetrahydrofuran was added to the resultant crude product, to thereby dissolve the crude product therein. The resultant mixture was stirred at 25°C for 10 minutes, and then subjected to filtration, to thereby — separate the mixture into a filtrate and a residue. Thereafter, tetrahydrofuran was removed from the filtrate with an evaporator, and 276.18 g of toluene was added to the resultant crude product. The resultant mixture was stirred at 25°C for 10 minutes, and then subjected to filtration, to thereby separate the mixture into a filtrate and a residue. Thereafter, toluene was removed from the filtrate with an evaporator, to thereby prepare a — target product; i.e., to-be-purified alkoxysilicon compound (A) (ICA-TEOS) as a pale yellow solid (yield: 43.2%).O
    [0031] [0031] <Purification of To-Be-Purified Alkoxysilicon Compound (A) with Chelate Resin> The chelate resins used in Examples and Comparative Examples are as follows. 5 , |
    [0032] [0032] [Example 1] The alkoxysilicon compound (A) prepared in Synthesis Example 1 was diluted with PGME to thereby prepare a 1% by weight solution. To 10 g of this solution was added 1 g of chelate resin S914 (trade name) having a thiourea group (available from Purolite), and the mixture was stirred at room temperature for four hours and then filtered, to thereby prepare a solution of the purified alkoxysilicon compound. The solution was subjected to GC for measurement of the amount of adsorption and to inductively coupled plasma mass spectrometry (ICP-MS 7500, available from Agilent Technologies, Inc.) for measurement of the amount of remaining Pt. Table 1 shows the results of measurement of the amount of adsorption and the amount of remaining Pt. The amount of remaining Pt corresponds to a value in terms of 100% by weight of the alkoxysilicon compound.
    [0033] [0033] [Example 2] The same treatment as in Example 1 was performed, except that the chelate resin available from Purolite was replaced with chelate resin S920 having a thiouronium group (available from Purolite). The results are shown in Table 1.
    [0034] [0034] [Example 3] The same treatment as in Example 1 was performed, except that the chelate resin available from Purolite was replaced with chelate resin Muromac XMS-5418 (trade name) having a thiouronium group (available from MUROMACHI CHEMICALS INC.). The S results are shown in Table 1. g [0035] — [Example4] N The same treatment as in Example 3 was performed, except that the to-be-purified = 25 — alkoxysilicon compound (A) prepared in Synthesis Example 1 was diluted with & cyclopentyl methyl ether (CPME) serving as a diluent solvent in place of PGME, to S thereby prepare a 1% by weight solution. The results are shown in Table 1. N [0036] [Comparative Example 1] The same treatment as in Example 1 was performed, except that the chelate resin available from Purolite was replaced with chelate resin CRB03 (trade name) having an N- methyl-glucamine group (available from Mitsubishi Chemical Corporation). The amount of adsorption was measured in the resultant solution. The results indicated that 44% of ICA-TEOS was adsorbed onto CRB03.
    [0037] [0037] [Comparative Example 2] The same treatment as in Example 1 was performed, except that the chelate resin available from Purolite was replaced with chelate resin CR20 (trade name) having a polyamine group (available from Mitsubishi Chemical Corporation). The amount of adsorption was measured in the resultant solution. The results indicated that 15% of ICA- TEOS was adsorbed onto CR20.
    [0038] [0038] [Comparative Example 3] The same treatment as in Example 1 was performed, except that the chelate resin available from Purolite was replaced with chelate resin IRC748 (trade name) having an iminodiacetate group (available from ORGANO CORPORATION). Theresultant — solution showed white turbidity and failed to undergo post-treatment.
    [0039] [0039] [Comparative Example 4] The same treatment as in Example 1 was performed, except that the chelate resin available from Purolite was replaced with chelate resin IRC747UPS (trade name) having an aminophosphate group (available from ORGANO CORPORATION). The resultant — solution showed white turbidity and failed to undergo post-treatment.ONO
    [0040] [0040] Table 1 Diluent | Chelate Amount of Rate of Amount of solvent resin remaining Pt | removal of Pt | alkoxysilicon compound (ppm) (%) (A) adsorbed onto chelate resin (%)PGME
    [0041] [0041] — As shown in Table 1, when each of the chelate resins of Examples 1 to 4 was used, platinum was able to be removed while reducing the amount of the alkoxysilicon compound adsorbed onto the chelate resin. In contrast, when each of the chelate resins of Comparative Examples 1 and 2 was used, a large amount of the alkoxysilicon compound was adsorbed onto the chelate resin; i.e., the chelate resin was found to be impractical. Meanwhile, when each of the chelate resins of Comparative Examples 3 and 4 was used, the resultant solution showed white turbidity, and post-treatment for removal of the metal — failed to be performed.ONON
    O <Q +N
    I a aOONLOONON
    权利要求:
    Claims (11)
    [1] 1. A method for purifying an alkoxysilicon compound, the method being characterized by comprising treating a to-be-purified alkoxysilicon compound containing a metal impurity with a chelate resin having a functional group containing a sulfur atom and a nitrogen atom.
    [2] 2. The method for purifying an alkoxysilicon compound according to claim 1, wherein the functional group is represented by any of the following Formulae (1-1) to (1- 3):
    S NH NH KUN Ks wi sn (1-1) (1-2) (1-3) (in Formulae (1-1) to (1-3), * is an end bonding to a resin serving as a carrier).
    [3] 3. The method for purifying an alkoxysilicon compound according to claim 1 or 2, characterized in that the to-be-purified alkoxysilicon compound containing a metal impurity is treated with a mixture containing the chelate resin or a mixture of the chelate S resin and an additional chelate resin. 8 20 N
    [4] 4. The method for purifying an alkoxysilicon compound according to claim 1 or 2, E characterized in that the to-be-purified alkoxysilicon compound containing a metal & impurity is treated one by one with two or more selected from the group consisting of the S chelate resin, a mixture containing the chelate resin, an additional chelate resin, and a N 25 — mixture of the chelate resin and the additional chelate resin.
    [5] 5. The method for purifying an alkoxysilicon compound according to any one of claims 1 to 4, wherein the alkoxysilicon compound has a molecular weight of 5,000 or less.
    [6] 6. The method for purifying an alkoxysilicon compound according to any one of claims 1 to 5, wherein the alkoxysilicon compound is prepared by reaction of a compound having a hydroxy group, an amino group, or an aryl group with an alkoxysilicon compound in the presence of a transition metal catalyst.
    [7] 7. The method for purifying an alkoxysilicon compound according to claim 6, wherein the alkoxysilicon compound is prepared by reaction of a compound having an aryl group with an alkoxysilicon compound having an Si-H bond in the presence of a transition metal catalyst.
    [8] 8. The method for purifying an alkoxysilicon compound according to claim 7, wherein the alkoxysilicon compound having an Si-H bond is a trialkoxysilane compound.
    [9] 9. The method for purifying an alkoxysilicon compound according to any one of claims 1 to 8, wherein the alkoxysilicon compound is prepared by reaction of an isocyanuric acid derivative having an aryl group with an alkoxysilicon compound having — an Si-H bond.
    S O
    [10] 10. An alkoxysilicon compound prepared by treatment of a to-be-purified g alkoxysilicon compound containing a metal impurity with a chelate resin having a N functional group containing a sulfur atom and a nitrogen atom, wherein the amount of the
    I = 25 remaining metal impurity is 1 ppm or less relative to 100% by weight of the alkoxysilicon
    O O compound.
    N
    LO
    O
    N
    N
    [11] 11. The alkoxysilicon compound according to claim 10, wherein the remaining metal is any of Pt, Ir, Re, Ni, Mo, Fe, Ti, Ca, and Sr.
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    同族专利:
    公开号 | 公开日
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP2019063479|2019-03-28|
    JP2020033966A|JP2020164506A|2019-03-28|2020-02-28|Method for purifying alkoxysilicon compound|
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