WO2016017387A1 - Procédé de séparation et de récupération alkylèneglycolmonoalkyléther, procédé de recyclage de déchets liquides provenant du traitement d'une composition de résine photosensible et procédé de recyclage d'un liquide de traitement d'une composition de résine photosensible - Google Patents

Procédé de séparation et de récupération alkylèneglycolmonoalkyléther, procédé de recyclage de déchets liquides provenant du traitement d'une composition de résine photosensible et procédé de recyclage d'un liquide de traitement d'une composition de résine photosensible Download PDF

Info

Publication number
WO2016017387A1
WO2016017387A1 PCT/JP2015/069667 JP2015069667W WO2016017387A1 WO 2016017387 A1 WO2016017387 A1 WO 2016017387A1 JP 2015069667 W JP2015069667 W JP 2015069667W WO 2016017387 A1 WO2016017387 A1 WO 2016017387A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
resist composition
waste liquid
glycol monoalkyl
monoalkyl ether
Prior art date
Application number
PCT/JP2015/069667
Other languages
English (en)
Japanese (ja)
Inventor
泰広 三河
不二麿 緒方
Original Assignee
昭和電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to CN201580033942.2A priority Critical patent/CN106660914B/zh
Priority to JP2016538245A priority patent/JP6602301B2/ja
Publication of WO2016017387A1 publication Critical patent/WO2016017387A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor

Definitions

  • the present invention relates to a method for separating and recovering an alkylene glycol monoalkyl ether, a method for reusing a resist composition treatment waste liquid, and a method for recycling a resist composition treatment liquid. More specifically, a solvent mixture containing an alkylene glycol monoalkyl ether and its corresponding carboxylic acid ester, for example, a method for separating and recovering an alkylene glycol monoalkyl ether from a treatment waste solution of a resist composition, and reuse of a resist composition treatment waste solution The present invention relates to a method and a method for recycling a resist composition treatment liquid.
  • a lithography technique using a conventional liquid photosensitive composition (hereinafter also referred to as “resist”) has been used.
  • a substrate such as a semiconductor (silicon substrate, etc.), glass, resin (polyimide, polyester, etc.) to form a pattern
  • the liquid photosensitive composition adhered to the edge or back surface of the substrate.
  • an apparatus for applying the liquid photosensitive composition or cleaning for removing the liquid photosensitive composition adhering to the surface of the member is required.
  • the waste solvent produced by washing the liquid photosensitive composition using the solvent mixture is mixed with resin, solvent, and other additives that are constituents of the liquid photosensitive composition. It will be. However, it is strongly desired to reuse the waste solvent, that is, to separate and recover the active ingredient from the waste solvent and reuse it from the viewpoint of environmental problems that have been attracting attention in recent years and the reduction of manufacturing costs.
  • Distillation is used as the most typical method for separating and recovering solvent components from a solvent mixture containing multiple components.
  • each component in the waste solvent is separated and purified by distillation. This is not only complicated, but also economically difficult.
  • alkylene glycol monoalkyl ether and alkylene glycol monoalkyl ether monocarboxylic acid ester have relatively close boiling points, it is difficult to separate and recover each with high purity and high recovery rate.
  • the component having a relatively low boiling point Separating lower components (low boiling fraction) than glycol monoalkyl ether) and higher components (high boiling fraction) having higher boiling points (alkylene glycol monoalkyl ether monocarboxylic acid ester)
  • a third component having a boiling point between two components it is difficult to separate only the third component.
  • Patent Document 1 as a solvent recycling method for resist resin alcohol / ester solvent, water is added to a resist solvent composed of alcohol and a corresponding ester to cause hydrolysis of the ester, and the amount of alcohol is determined. It is disclosed to increase the amount before hydrolysis and then purify the resulting reaction mass by distillation.
  • Patent Document 2 B component in a solvent mixture containing alkylene glycol monoalkyl ether (A component) and A component acetate ester (B component) is converted to A component by transesterification, and the solvent mixture is distilled. Thus, it is disclosed that component A is separated and recovered.
  • Patent Document 1 discloses that the ratio of ester / alcohol in the solvent mixture can be arbitrarily adjusted by esterification reaction of alcohol by addition of carboxylic acid or hydrolysis of ester, but in the examples, by addition of carboxylic acid. Components other than the target ester and alcohol contained in the waste liquid before esterification reaction or before hydrolysis are very small amounts of 0.3%, and the coexistence of other components is carried out under almost no consideration. ing. That is, Patent Document 1 discloses only controlling the mixing ratio of both in a mixed solution containing substantially two components of ester / alcohol. In Patent Document 2, a transesterification reaction is used. However, since the transesterification reaction is an equilibrium reaction, it is difficult to convert 100% of the B component to the A component, and thus it is difficult to obtain a high yield.
  • the present invention separates and recovers alkylene glycol monoalkyl ether in high purity and high yield from a solvent mixture containing alkylene glycol monoalkyl ether and its corresponding carboxylic acid ester and containing other solvents.
  • One of the purposes is to provide a method to do this.
  • Another object of the present invention is to provide a method for reusing a processing waste liquid of a resist composition containing an alkylene glycol monoalkyl ether and its corresponding carboxylic acid ester and a method for recycling a resist composition processing liquid.
  • a first solvent represented by the following general formula (I), a second solvent represented by the following general formula (II), and the third solvent different from the first solvent and the second solvent A first solvent mixture comprising a first solvent mixture, wherein the first solvent is separated and recovered, A first step of obtaining a second solvent mixture obtained by saponifying the second solvent and converting it to the first solvent by adding an alkali compound to the first solvent mixture; A second step of distilling the second solvent mixture to recover the first solvent; A method for separating and recovering an alkylene glycol monoalkyl ether, comprising: [In the general formulas (I) and (II), R represents an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkylene group having 2 to 4 carbon atoms, and R ′′ represents an alkyl group having 1 to 2 carbon atoms.
  • R and R ′ are the same, and n is 1 or 2.
  • the alkali compound is at least one alkali hydroxide compound selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide. Separation and recovery method.
  • the first solvent is propylene glycol monomethyl ether
  • the second solvent is propylene glycol monomethyl ether acetate
  • the third solvent is cyclopentanone, cyclohexanone, and methyl-3-methoxypropionate.
  • the method for separating and recovering an alkylene glycol monoalkyl ether according to any one of [1] to [3], which is at least one selected from the group consisting of: [5] Any one of [1] to [4], wherein the first solvent mixture is a processing waste liquid obtained by treating the resist composition with a mixed solvent containing the first solvent and the second solvent.
  • R and R ′ are the same, and n is 1 or 2.
  • the alkali compound is at least one alkali hydroxide compound selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide.
  • the alkali compound is sodium hydroxide.
  • Reuse method of composition processing waste liquid [11] A user purchases from a manufacturer a mixed solvent containing a first solvent represented by the following general formula (I) and a second solvent represented by the following general formula (II) in a predetermined blending ratio.
  • a second step in which a user processes the resist composition using the mixed solvent A third step in which the manufacturer or recovery company collects the processing waste liquid generated in the second step; and a second solvent in the processing waste liquid by the manufacturer or the recovery company adding an alkali compound to the processing waste liquid.
  • a fourth step of saponifying and converting to a first solvent A fifth step of recovering the first solvent by distilling the solvent mixture obtained in the fourth step by the manufacturer or the collector; A sixth step of re-preparing the mixed solvent having the predetermined mixing ratio by adding a new second solvent to the first solvent recovered in the fifth step by the manufacturer or the collector; A seventh step in which a user purchases the re-prepared mixed solvent from a manufacturer or a collector, and the resist composition treatment is performed repeatedly from the second step to the seventh step Liquid recycling method.
  • R represents an alkyl group having 1 to 4 carbon atoms
  • R ′ represents an alkylene group having 2 to 4 carbon atoms
  • R ′′ represents an alkyl group having 1 to 2 carbon atoms.
  • R and R ′ are the same, and n is 1 or 2.
  • the alkali compound is at least one alkali hydroxide compound selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide. Recycling method.
  • alkylene glycol monoalkyl ether can be separated and recovered with high purity and high yield from a solvent mixture containing alkylene glycol monoalkyl ether and its corresponding carboxylic acid ester and other solvents.
  • alkylene glycol monoalkyl ether can be separated and recovered in high purity and high yield from a processing waste solution of a resist composition containing alkylene glycol monoalkyl ether and its corresponding carboxylic acid ester and other solvents. Therefore, according to the present invention, it is possible to manufacture a semiconductor element, a liquid crystal display element, a color filter and the like at a low cost by reusing a processing waste liquid of the resist composition.
  • a first embodiment of the present invention includes an alkylene glycol monoalkyl ether (first solvent), an alkylene glycol monoalkyl ether carboxylic acid ester (second solvent), an alkylene glycol monoalkyl ether ( An alkylene glycol monoalkyl ether from a solvent mixture (first solvent mixture) comprising a first solvent) and a different solvent (third solvent) than the alkylene glycol monoalkyl ether carboxylic acid ester (second solvent). This is a method for separating and collecting the first solvent).
  • a first solvent mixture is obtained by adding an alkali compound to the first solvent mixture to saponify the alkylene glycol monoalkyl ether carboxylic acid ester in the first solvent mixture and convert it to an alkylene glycol monoalkyl ether. And a second step of separating and recovering the alkylene glycol monoalkyl ether by distilling the second solvent mixture.
  • the first solvent mixture to be separated and recovered is an alkylene glycol monoalkyl ether (first solvent) represented by the following general formula (I) and the following general formula (II):
  • An alkylene glycol monoalkyl ether carboxylic acid ester (second solvent) which is a corresponding carboxylic acid ester of the first solvent represented by the formula (1), and at least one solvent other than these two solvents (third Solvent).
  • R represents an alkyl group having 1 to 4 carbon atoms
  • R ′ represents an alkylene group having 2 to 4 carbon atoms
  • R ′′ represents an alkyl group having 1 to 2 carbon atoms.
  • R and R ′ are the same, and n is 1 or 2.
  • the first solvent mixture contains, as essential components, the first solvent and the second solvent represented by the general formula (I) and the general formula (II), respectively, and at least other than these two solvents.
  • the present invention is not particularly limited as long as it contains one kind of solvent (third solvent), but in the present invention, the boiling point of the third solvent is between the boiling point of the first solvent and the second solvent. Is particularly effective.
  • a waste solvent of a mixed organic solvent used as a solvent for removing a resist composition, a solvent for cleaning, and the like is an object of separation and recovery.
  • R examples include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl groups.
  • R ′ examples include ethylene group, trimethylene group, propylene group, butylene group and the like.
  • R and R 'in general formula (I) and general formula (II) are the same.
  • R ′′ in the general formula (II) is a methyl group or an ethyl group.
  • N is 1 or 2.
  • the first solvent represented by the general formula (I) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol. Examples thereof include monomethyl ether and dipropylene glycol monomethyl ether.
  • the second solvent represented by the general formula (II) include those acetates and propionates.
  • the first solvent mixture is a mixture containing a first solvent and a second solvent, and includes a mixed solution containing ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether and ethylene glycol monoethyl ether acetate.
  • the separation and recovery method of the present invention can be suitably applied to a solvent mixture containing propylene glycol monomethyl ether as the first solvent and propylene glycol monomethyl ether acetate as the second solvent.
  • the content ratio of the first solvent and the second solvent in the first solvent mixture is not particularly limited as long as these two components are mixed, but preferably the first solvent and the second solvent.
  • the mixing ratio (first solvent / second solvent) in terms of mass is 1 or more, more preferably 1.5 or more, and still more preferably 2 or more.
  • the content ratio of the second solvent is smaller, the amount of alkali compound (sodium hydroxide, etc.) required for the saponification reaction of the second solvent, which will be described later, can be reduced, and the alkali compound can be made more uniform in the solvent mixture. Can be dispersed.
  • the first solvent mixture contains at least one third solvent other than the first solvent and the second solvent.
  • the solvent blended in the resist composition can be the third solvent.
  • the third solvent include ketones such as cyclopentanone and cyclohexanone, and esters such as ethyl lactate and methyl-3-methoxypropionate.
  • the first solvent mixture may contain components other than the solvent.
  • the waste liquid used for stripping or washing the resist composition generally contains a resin derived from the resist composition, additives (curing agents, pigments, etc.), and the like.
  • the present invention converts the second solvent in the first solvent mixture into the first solvent in the first step. Apply a saponification reaction to achieve this.
  • the saponification reaction can be carried out by adding an alkali compound, preferably any one alkali hydroxide compound selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide.
  • an alkali compound preferably any one alkali hydroxide compound selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide.
  • the saponification reaction in the case of using sodium hydroxide is represented by the following reaction formula (III).
  • R represents an alkyl group having 1 to 4 carbon atoms
  • R ′ represents an alkylene group having 2 to 4 carbon atoms
  • R ′′ represents an alkyl group having 1 to 2 carbon atoms
  • n is 1 or 2.
  • the amount of the alkali compound used in the saponification reaction is 0.8 to 1.2 molar equivalents, preferably 0.9 to 1.1 molar equivalents relative to the second solvent contained in the first solvent mixture.
  • the amount is preferably 0.95 to 1.05 molar equivalent.
  • the amount of the alkali compound is less than 0.8 molar equivalent, the residual amount of the second solvent that is not converted to the first solvent increases and the yield decreases.
  • the amount of the alkali compound is more than 1.2 molar equivalent, not only the amount that does not contribute to the saponification reaction is increased, but also it is disadvantageous in uniformly dispersing in the first solvent mixture.
  • sodium hydroxide, potassium hydroxide, or calcium hydroxide When sodium hydroxide, potassium hydroxide, or calcium hydroxide is used as the alkali compound, these alkali hydroxide compounds have low solubility in the first solvent mixture, and thus it is desirable to stir them so that they are uniformly dispersed.
  • Calcium hydroxide has a lower solubility in water than sodium hydroxide and potassium hydroxide, and the reaction rate is slower by that amount.
  • a ketone solvent such as cyclopentanone or cyclohexanone
  • the use of an alkali hydroxide compound causes dimerization (aldol condensation) of these ketone solvents, resulting in higher boiling point dimerization. A quantified product is formed.
  • propylene glycol monomethyl ether when the component to be recovered is propylene glycol monomethyl ether and the ketone solvent is cyclopentanone (131 ° C.) having a boiling point relatively close to that of propylene glycol monomethyl ether (120 ° C.), propylene glycol monomethyl A dimerization product (boiling point> 160 ° C.) of a ketone solvent having a larger boiling point difference from ether can be produced and easily separated from propylene glycol monomethyl ether.
  • potassium hydroxide has the same degree of reactivity as sodium hydroxide, it is more expensive than sodium hydroxide. Calcium hydroxide is less expensive but less reactive, so it is preferable to use sodium hydroxide. .
  • Ammonium hydroxide can also be used, but when heated, it volatilizes as ammonia, which may not be desirable when the reaction reaches a high temperature.
  • the alkali hydroxide compound can also be used as an aqueous solution.
  • the use as an aqueous solution is advantageous from the viewpoint of uniform mixing into a solvent mixture, but the yield is disadvantageous because the solvent to be separated and recovered in the distillation step described below azeotropes with water. Therefore, it is preferable to suppress the addition of water to a necessary minimum (for example, when sodium hydroxide is used as an aqueous solution, use 48% by mass or more).
  • the resist composition may contain a carboxylic acid ester other than the carboxylic acid ester represented by the general formula (II). May undergo a saponification reaction in the same manner as the carboxylic acid ester represented by the general formula (II) to consume an alkali compound. Therefore, when a carboxylic acid ester other than the carboxylic acid ester represented by the general formula (II) is contained in the first solvent mixture, the above-mentioned definition is made with respect to the total amount of carboxylic acid ester contained in the first solvent mixture. It is preferable to use an alkali compound in the range of.
  • Saponification reaction conditions are not particularly limited, but the temperature is preferably in the range of room temperature to 100 ° C., and the time is preferably in the range of 1 to 10 hours.
  • the reaction atmosphere is not particularly limited and can be carried out in the air or under an inert atmosphere (nitrogen, argon, etc.).
  • an atmosphere having a low humidity for example, relative The humidity is preferably 50% or less, more preferably 10 to 40%.
  • the second solvent mixture is distilled in order to separate and recover the first solvent from the solvent mixture (second solvent mixture) obtained after the saponification reaction.
  • the second solvent mixture contains the carboxylate formed by the saponification reaction. Since the carboxylate is hardly dissolved in the solvent mixture (second solvent mixture), if the carboxylate is distilled in a state where it is contained in the second solvent mixture, the carboxylate precipitates during the distillation operation and the distillation equipment is installed. May be contaminated. Therefore, it is preferable to provide the process of isolate
  • the separation step is not particularly limited as long as the carboxylate salt can be separated, and known methods such as evaporation separation, filtration separation, and centrifugal separation can be applied, but the ratio of the solvent contained in the solid (carboxylate salt) is lowered, It is desirable to use a thin film evaporator for efficient and efficient discharge.
  • Thin-film distillation is an evaporator that increases the evaporation efficiency by forming a thin film of solution on the wall of a cylinder.
  • Shinba Environmental Solution Co., Ltd. Exeva registered trademark
  • Kimura Chemical Co., Ltd. forced sales expansion type evaporator And High Evaporator (registered trademark) of Sakai Seisakusho Co., Ltd.
  • the thin film distillation can be carried out under normal pressure, but it is advantageous from the viewpoint of securing a supply heat source, etc., preferably under reduced pressure of about 100 to 300 torr.
  • the solid components contained in the processing waste liquid are also simultaneously separated in the separation step. Separation of these solid components can be carried out before the saponification reaction of the first solvent mixture, but since the separation step of the carboxylate formed after the saponification reaction may be necessary again, the saponification reaction It is advantageous to separate with the carboxylate later.
  • the distillation method and distillation apparatus for the second solvent mixture are not particularly limited.
  • the distillation technique any conventionally known technique such as atmospheric distillation or vacuum distillation can be applied. Any of various known distillation apparatuses such as a continuous type and a batch type can be applied.
  • a component having a lower boiling point than the first solvent (low boiling fraction) is distilled off by distillation, and then the first solvent is recovered.
  • the second solvent can be converted to the first solvent by a saponification reaction and separated and recovered from the third solvent.
  • the conditions for separating and recovering the first solvent by distillation are not particularly limited, but after refluxing for about 10 minutes to 2 hours at a temperature about the boiling point of the first solvent, the first solvent is distilled. It is preferable to isolate them. Such an operation makes it possible to recover the first solvent with high purity.
  • the third solvent is a ketone solvent having a boiling point close to that of the first solvent
  • the ketone solvent is dimerized by aldol condensation during the saponification reaction of the first solvent mixture. Since a dimer having a larger difference in boiling point from that of the above solvent is produced, the first solvent can be easily separated and recovered with high purity.
  • high-purity alkylene glycol monoalkyl ether is efficiently obtained from a solvent mixture containing at least one alkylene glycol monoalkyl ether and its corresponding carboxylic acid ester and other solvents. It can be separated and recovered.
  • the second embodiment of the present invention is an alkylene glycol monoalkyl ether carboxylic acid ester (second solvent) which is a corresponding carboxylic acid ester of an alkylene glycol monoalkyl ether (first solvent) and the first solvent. And a waste solution obtained by treating a resist composition using a mixed solvent containing a solvent.
  • the waste liquid used in the second embodiment is equivalent to the processing waste liquid of the resist composition described in the first embodiment. Accordingly, the third step and the fourth step in the second embodiment correspond to the first step and the second step in the first embodiment, respectively, and thus description thereof is omitted.
  • the first step in the second embodiment is a resist composition using a mixed solvent containing a solvent represented by the general formula (I) and the general formula (II), such as a solvent for removing the resist composition, a solvent for cleaning, and the like. For example, washing or rinsing. More specifically, in a manufacturing process of a semiconductor element, a liquid crystal display element, a color filter, etc., an unnecessary resist composition attached to a semiconductor substrate or a glass substrate, or a nozzle or a pipe of an apparatus for applying the resist composition to the substrate This is a step of removing the resist composition adhering to the surface.
  • a solvent represented by the general formula (I) and the general formula (II) such as a solvent for removing the resist composition, a solvent for cleaning, and the like. For example, washing or rinsing. More specifically, in a manufacturing process of a semiconductor element, a liquid crystal display element, a color filter, etc., an unnecessary resist composition attached to a semiconductor substrate or a glass substrate, or
  • the solvent for removing and the solvent for cleaning of the resist composition are substantially free of a third solvent other than the solvents represented by general formula (I) and general formula (II).
  • substantially free means that the third solvent is not intentionally added, and impurities are contained within a range that satisfies the product standards of the resist solvent for the resist composition and the solvent for cleaning. Except when including.
  • the second step in the second embodiment is a step of recovering the processing waste liquid containing the resist composition generated in the first step.
  • the fifth step in the second embodiment has a predetermined blending ratio desirable for the intended use by newly adding the second solvent to the first solvent separated and recovered in the fourth step.
  • This is a step of re-preparing the mixed solvent.
  • An example is a step of adding a predetermined amount of a second solvent so that the resist composition used in the first step has the same composition as the solvent for removal or cleaning, but it is used in other applications. It is also possible to adjust the composition to a different composition ratio.
  • the first solvent having a high purity is efficiently recovered from the waste liquid treated with the resist composition, and a predetermined amount of the second solvent is newly added.
  • the stripping solvent, cleaning solvent, etc. of the composition can be re-prepared, that is, the processing waste liquid can be effectively reused.
  • the treatment waste liquid (solvent mixture) is directly distilled to have a higher purity than the conventional method of separating and removing a fraction having a lower boiling point than the first solvent and a fraction having a higher boiling point than the second solvent.
  • a mixed solvent can be obtained at low cost.
  • a third embodiment is a method for recycling a resist composition processing solution. Regarding recovery of the first solvent from the resist composition processing waste liquid and re-preparation of a mixed solvent having a predetermined blending ratio by newly adding a second solvent, for example, a resist composition stripping solvent or a cleaning solvent Since it is equivalent to a 2nd embodiment, the overlapping description is abbreviate
  • the processing waste liquid recovery process third process
  • reaction process fourth process
  • distillation process fifth process
  • a solvent manufacturer or a recovery company collects a plurality of users and performs processing collectively.
  • the solvent manufacturer performs processing
  • the newly prepared second solvent is blended with the first solvent that has been processed and separated and recovered so as to meet the specifications of the resist composition processing solution.
  • the mixed solution can be re-prepared.
  • the manufacturer or the collector After the user purchases the resist composition processing solution from the manufacturer (first step) and the user performs the processing of the resist composition (second step), the manufacturer or the collector The third to sixth steps are performed, and the user purchases the re-prepared mixed solvent from the manufacturer or the collector (seventh step), and thereafter the second to seventh steps are repeatedly performed.
  • Example 1 As a solvent mixture containing alkylene glycol monoalkyl ether (first solvent) and its corresponding carboxylic acid ester (second solvent) and other solvent (third solvent), propylene glycol having the composition shown in Table 1 below A solvent mixture (first solvent mixture) containing monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and other solvents was prepared.
  • a saponification reaction of a solvent mixture having the composition described in Table 1 was carried out. Specifically, 793 g of a solvent mixture (first solvent mixture) having the composition shown in Table 1 and 94 g of sodium hydroxide were charged into a 1-liter three-necked flask equipped with a reflux condenser and a stirring device. Was heated to 80 ° C. at normal pressure while flowing nitrogen, and held for 3 hours to carry out a saponification reaction. After the reaction, the solvent mixture (second solvent mixture) is allowed to cool to room temperature and then subjected to simple distillation to separate it from solids (sodium acetate) with an evaporator, followed by distillation to obtain the target product (PGME). I went again.
  • the Oldershaw distillation apparatus 10 shown in FIG. 1 was used as the distillation apparatus.
  • A is a 1 L flask equipped with a thermometer 15
  • B is a rectifying column having 20 theoretical plates.
  • the vapor rising to the top of the column is condensed in the reflux head 11 and the reflux ratio can be adjusted by the reflux / distillation switching funnel 12 operated by a solenoid valve.
  • a distillation cock 13 was disposed on the distillation side, and a receiver 14 was prepared at the end.
  • the simple distillation recovery liquid obtained above was put into Flask A, and the distillate was fractionated after heating and refluxing for 2 hours.
  • Table 1 shows the results of gas chromatography (GC) analysis of the solvent mixture, simple distillation recovery liquid and distillation recovery liquid described in Table 1 above.
  • the recovery rate by distillation in the simple distillation recovery liquid is the ratio of the mass of the simple distillation recovery liquid to the mass of the original solvent mixture used (first solvent mixture), and the PGME in the simple distillation recovery liquid.
  • the recovery rate is the ratio of the PGME mass in the simple distillation recovery liquid to the sum of the PGME mass and the PGMEA mass in the original solvent mixture (first solvent mixture) used.
  • the recovery rate by distillation in the distillation recovery liquid is the ratio of the mass of the final distillation recovery liquid to the mass of the original solvent mixture (first solvent mixture) used.
  • What is the PGME recovery rate in the distillation recovery liquid? The ratio of the PGME mass in the final distillation recovery liquid to the sum of the PGME mass and the PGMEA mass in the original solvent mixture (first solvent mixture) used.
  • GC gas chromatography
  • Comparative Example 1 A solvent mixture obtained by adding 65 g of water to 714 g of the solvent mixture of Example 1 was heated and refluxed for 21 hours using a distillation apparatus in the same manner as in Example 1, and the distillate was collected and recovered. The rate was calculated and the purity of the distillate was confirmed by gas chromatography. The measurement conditions for gas chromatography are the same as in Example 1. The recovery rate and purity obtained are shown in Table 2. The PGME recovery rate was calculated by the following formula. The amount of water added is 65 g, and the third component (MMP and CYP) in the solvent mixture is the lowest azeotrope (the mixture when the boiling point of the azeotrope, that is, the azeotropic temperature takes a minimum value on the boiling point curve).
  • Comparative Example 2 To the solvent mixture obtained by adding 138 g of methanol to 700 g of the solvent mixture of Example 1, about 0.8 g (0.01 times mol of PGMEA in the solvent mixture) using sodium methoxide as a catalyst was added. After a reaction at 190 ° C. for 190 minutes until normal pressure, using a distillation apparatus in the same manner as in Comparative Example 1, after heating and refluxing for 2 hours, the distillate was collected, and its recovery rate was calculated. The purity of the product was confirmed by gas chromatography. The recovery rate and purity obtained are shown in Table 2.
  • the amount of methanol added 138 g was determined in consideration of the conversion rate of the transesterification reaction and the energy cost based on the subsequent separation process, and corresponds to a 3-fold molar amount of PGMEA in the solvent mixture. Equilibrium under the above conditions was confirmed by sampling over time and having a constant composition by gas chromatography. Even in this comparative example, there is no process corresponding to the simple distillation in Example 1.
  • Comparative Example 3 The solvent mixture of Example 1 was heated and refluxed for 2 hours using a distillation apparatus without carrying out a saponification reaction, and then the distillate was collected, the recovery rate was calculated, and the purity of the distillate was determined. Confirmed by gas chromatography. The recovery rate and purity obtained are shown in Table 2. Even in this comparative example, there is no process corresponding to the simple distillation in Example 1.
  • Comparative Example 4 700 g containing only propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is used as a solvent mixture, to which 33 g of sodium hydroxide and 14 g of water are added and subjected to a hydrolysis reaction at 120 ° C. for 4 hours at normal pressure. After 21 hours of heating under reflux, the distillate was collected and the recovery rate was calculated. Even in this comparative example, there is no process corresponding to the simple distillation in Example 1.
  • Comparative Example 4 shows that a high-purity product can be obtained in a high yield, but no other impurities other than propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA) are contained in the solvent mixture As a result, PGME does not bring any knowledge about the ease of separation of PGME from other impurities.
  • PGME propylene glycol monomethyl ether
  • PGMEA propylene glycol monomethyl ether acetate
  • alkylene glycol monoalkyl ether can be separated and recovered with high purity and high yield from a solvent mixture containing alkylene glycol monoalkyl ether and its corresponding carboxylic acid ester and other solvents.
  • INDUSTRIAL APPLICABILITY The present invention is effective as a method for reusing a processing solution waste liquid, and enables low-cost production of semiconductor elements, liquid crystal display elements, color filters, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un procédé pour séparer et récupérer, à une pureté élevée et à un taux de récupération élevé, de l'alkylèneglycolmonoalkyléther à partir d'un mélange de solvants contenant : de l'alkylèneglycolmonoalkyléther ; un ester d'acide carboxylique correspondant à celui-ci ; et d'autres solvants. Par addition d'un composé alcalin à un mélange de solvants qui contient : de l'alkylèneglycolmonoalkyléther (premier solvant) ; de l'ester d'acide carboxylique de l'alkylèneglycolmonoalkyléther (deuxième solvant) correspondant à l'alkylèneglycolmonoalkyléther (premier solvant) ; et un solvant (troisième solvant) autre que l'alkylèneglycolmonoalkyléther (premier solvant) et que l'ester d'acide carboxylique de l'alkylèneglycolmonoalkyléther (deuxième solvant), l'ester carboxylique de l'alkylèneglycolmonoalkyléther (deuxième solvant) est saponifié et transformé en alkylèneglycolmonoalkyléther (premier solvant). Ensuite, l'alkylèneglycolmonoalkyléther (premier solvant) est récupéré par distillation.
PCT/JP2015/069667 2014-07-30 2015-07-08 Procédé de séparation et de récupération alkylèneglycolmonoalkyléther, procédé de recyclage de déchets liquides provenant du traitement d'une composition de résine photosensible et procédé de recyclage d'un liquide de traitement d'une composition de résine photosensible WO2016017387A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201580033942.2A CN106660914B (zh) 2014-07-30 2015-07-08 烷撑二醇单烷基醚的分离回收方法、抗蚀剂组合物处理废液的再利用方法和抗蚀剂组合物处理液的循环使用方法
JP2016538245A JP6602301B2 (ja) 2014-07-30 2015-07-08 アルキレングリコールモノアルキルエーテルの分離回収方法、レジスト組成物処理廃液の再利用方法及びレジスト組成物処理液のリサイクル方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014155104 2014-07-30
JP2014-155104 2014-07-30

Publications (1)

Publication Number Publication Date
WO2016017387A1 true WO2016017387A1 (fr) 2016-02-04

Family

ID=55217292

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/069667 WO2016017387A1 (fr) 2014-07-30 2015-07-08 Procédé de séparation et de récupération alkylèneglycolmonoalkyléther, procédé de recyclage de déchets liquides provenant du traitement d'une composition de résine photosensible et procédé de recyclage d'un liquide de traitement d'une composition de résine photosensible

Country Status (4)

Country Link
JP (1) JP6602301B2 (fr)
CN (1) CN106660914B (fr)
TW (1) TWI588123B (fr)
WO (1) WO2016017387A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180425B (zh) * 2018-10-29 2024-03-19 江阴市大洋固废处置利用有限公司 含环戊酮和丙二醇甲醚醋酸酯回收液的精制工艺及系统

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5195008A (ja) * 1975-02-14 1976-08-20 Echirengurikooruarukirueeteruno seiseihoho
JPS5589236A (en) * 1978-12-28 1980-07-05 Yotsukaichi Gosei Kk Purification of crude glycol ether
JPH01180844A (ja) * 1988-01-12 1989-07-18 Daicel Chem Ind Ltd ジグリセリンの精製方法
JPH01275544A (ja) * 1988-04-27 1989-11-06 Kyowa Yuka Kk グリコールエーテルの精製法
JPH08507764A (ja) * 1993-03-25 1996-08-20 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン ジグリセロールの製造方法
JPH08231991A (ja) * 1994-12-27 1996-09-10 Hitachi Ltd 洗浄用組成物、洗浄方法および洗浄液の製造方法
JP2001064221A (ja) * 1999-08-30 2001-03-13 Lion Corp 匂いの改良された（ポリ）エチレングリコールモノアルキルエーテル系溶剤及びその製造方法
JP2002045602A (ja) * 2000-08-07 2002-02-12 Mitsubishi Chemicals Corp 段塔式反応装置及びそれを用いたポリアルキレンエーテルグリコールの製造方法
JP2005247816A (ja) * 2004-03-08 2005-09-15 Sanwa Yuka Kogyo Kk アルキレングリコールモノアルキルエーテルの分離回収方法
JP2007178589A (ja) * 2005-12-27 2007-07-12 Tokyo Ohka Kogyo Co Ltd ホトリソグラフィ用洗浄液およびその循環使用方法
JP2011509998A (ja) * 2008-01-17 2011-03-31 ライオンデル ケミカル テクノロジー、 エル．ピー． プロピレングリコールモノアルキルエーテルの製造
JP2013506658A (ja) * 2009-09-30 2013-02-28 ウィズケム カンパニー・リミテッド １，４−二置換シクロヘキサン誘導体の製造方法
JP2013540171A (ja) * 2010-09-27 2013-10-31 イーストマン ケミカル カンパニー 基材から物質を除去するための方法および組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100944400B1 (ko) * 2005-07-19 2010-02-25 쇼와 덴코 가부시키가이샤 감광성 조성물용 제거액
KR100997743B1 (ko) * 2008-06-25 2010-12-01 덕산약품공업주식회사 포토레지스트 제거용 폐액으로부터 유기용제의 회수 방법
JP5433279B2 (ja) * 2009-03-31 2014-03-05 東京応化工業株式会社 再生レジストの製造方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5195008A (ja) * 1975-02-14 1976-08-20 Echirengurikooruarukirueeteruno seiseihoho
JPS5589236A (en) * 1978-12-28 1980-07-05 Yotsukaichi Gosei Kk Purification of crude glycol ether
JPH01180844A (ja) * 1988-01-12 1989-07-18 Daicel Chem Ind Ltd ジグリセリンの精製方法
JPH01275544A (ja) * 1988-04-27 1989-11-06 Kyowa Yuka Kk グリコールエーテルの精製法
JPH08507764A (ja) * 1993-03-25 1996-08-20 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン ジグリセロールの製造方法
JPH08231991A (ja) * 1994-12-27 1996-09-10 Hitachi Ltd 洗浄用組成物、洗浄方法および洗浄液の製造方法
JP2001064221A (ja) * 1999-08-30 2001-03-13 Lion Corp 匂いの改良された（ポリ）エチレングリコールモノアルキルエーテル系溶剤及びその製造方法
JP2002045602A (ja) * 2000-08-07 2002-02-12 Mitsubishi Chemicals Corp 段塔式反応装置及びそれを用いたポリアルキレンエーテルグリコールの製造方法
JP2005247816A (ja) * 2004-03-08 2005-09-15 Sanwa Yuka Kogyo Kk アルキレングリコールモノアルキルエーテルの分離回収方法
JP2007178589A (ja) * 2005-12-27 2007-07-12 Tokyo Ohka Kogyo Co Ltd ホトリソグラフィ用洗浄液およびその循環使用方法
JP2011509998A (ja) * 2008-01-17 2011-03-31 ライオンデル ケミカル テクノロジー、 エル．ピー． プロピレングリコールモノアルキルエーテルの製造
JP2013506658A (ja) * 2009-09-30 2013-02-28 ウィズケム カンパニー・リミテッド １，４−二置換シクロヘキサン誘導体の製造方法
JP2013540171A (ja) * 2010-09-27 2013-10-31 イーストマン ケミカル カンパニー 基材から物質を除去するための方法および組成物

Also Published As

Publication number Publication date
JPWO2016017387A1 (ja) 2017-05-18
TW201619105A (zh) 2016-06-01
TWI588123B (zh) 2017-06-21
CN106660914A (zh) 2017-05-10
JP6602301B2 (ja) 2019-11-06
CN106660914B (zh) 2019-06-04

Similar Documents

Publication Publication Date Title
JP6450470B2 (ja) 蒸留装置
CN102872679A (zh) 从制备(甲基)丙烯酸的工艺的废水物流中去除有机化合物的方法
JP2019509165A (ja) 加水分解性有機溶媒のための精製プロセス
KR20090089266A (ko) 에스테르계 용제의 제조 방법
JP6602301B2 (ja) アルキレングリコールモノアルキルエーテルの分離回収方法、レジスト組成物処理廃液の再利用方法及びレジスト組成物処理液のリサイクル方法
JP6630415B2 (ja) 高純度シクロヘキサシラン
KR101282799B1 (ko) Ｐｍａ를 재생하기 위한 유기용제의 정제 방법
CN112142630A (zh) 一种从半导体工业废液中回收二甲基亚砜的方法
JP4563052B2 (ja) アルキレングリコールモノアルキルエーテルの分離回収方法
JP4171570B2 (ja) 高純度アルキルアダマンチルエステルの製造方法
CN111620398B (zh) 含nmp的废剥离液回收方法、回收的剥离液及应用
KR102109403B1 (ko) 신너 폐액의 정제방법 및 그로부터 수득되는 신너 조성물
KR101427397B1 (ko) Ｐｍａ 정제방법
CN103080067B (zh) 有机溶剂的提纯方法
KR101232334B1 (ko) 유기용제의 정제 방법
KR102598771B1 (ko) 포토레지스트 공정에 사용되는 고순도 알킬렌글리콜 모노알킬 에테르 카르복실산 에스테르의 정제방법
JP2008297242A (ja) 高純度アルキルアダマンチル（メタ）アクリレートの製造方法
JP6008201B2 (ja) スチレン誘導体の製造方法
JP2001097893A (ja) 高純度有機化合物の製造方法
KR101371209B1 (ko) Ｐｍａ 재생 방법
KR100649411B1 (ko) 고순도 유기 화합물의 제조 방법
CN114989047A (zh) 一种从废有机溶剂中回收二甲基亚砜的方法
JP5498753B2 (ja) 脂環構造と芳香環構造とを併せもつビニルエーテル
JP2003238535A (ja) 高沸点物を除去することを特徴とする蒸留方法
TW201437196A (zh) 多官能（甲基）丙烯酸酯之製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15826782

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016538245

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15826782

Country of ref document: EP

Kind code of ref document: A1