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WO2020017779A1 - Method for purifying waste solution of thinner and thinner composition obtained therefrom - Google Patents

Method for purifying waste solution of thinner and thinner composition obtained therefrom Download PDF

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Publication number
WO2020017779A1
WO2020017779A1 PCT/KR2019/007786 KR2019007786W WO2020017779A1 WO 2020017779 A1 WO2020017779 A1 WO 2020017779A1 KR 2019007786 W KR2019007786 W KR 2019007786W WO 2020017779 A1 WO2020017779 A1 WO 2020017779A1
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thinner
boiling point
compound
weight
composition
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French (fr)
Korean (ko)
Inventor
이우용
이승용
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Duksan Co ltd
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Duksan Co ltd
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    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/3092—Recovery of material; Waste processing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/043—Details
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02076—Cleaning after the substrates have been singulated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02079—Cleaning for reclaiming
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the present invention relates to a method for purifying thinner waste liquid, and more particularly, it can be used in the rinsing process of the display manufacturing process using the waste liquid of the thinner used in the rinsing process of cleaning the photoresist during the semiconductor manufacturing process, and removes impurities.
  • the present invention relates to a method for purifying thinner waste liquid which can improve economic efficiency by using a purified product directly as a thinner composition without adding a specific compound or using a specific device other than distillation.
  • the photoresist cleaning thinner is used in a rinsing process for cleaning the remaining photoresist after exposure and etching in semiconductor or display manufacturing process.
  • the thinner is mixed with specific chemicals in a specific component ratio.
  • a thinner consisting of 70% by weight of 1-methoxy-2-propanol acetate and 30% by weight of 1-methoxy-2-propanol is typically used.
  • the conventional method for purifying thinner waste liquid has a problem in that an additional compound such as an alkali compound, benzoyl chloride, etc. is added to remove impurities in the thinner waste liquid, or impurities are separately removed using a separator in addition to the distillation process. .
  • the substance obtained by the conventional thinner waste liquid purification method cannot be used directly as a thinner, and there is a problem in that specific components must be further mixed.
  • the present invention has been made to solve the above problems,
  • the present invention provides a method for purifying thinner waste liquid which can obtain a thinner composition which can be used in the rinse process of the display manufacturing process by using the waste liquid used in the rinse process for cleaning the photoresist during the semiconductor manufacturing process. There is this.
  • the present invention provides a method for purifying thinner waste liquid which can improve economic efficiency by using a purified product directly as a thinner composition without adding a specific compound or using a specific device other than distillation to remove impurities.
  • the purpose is to provide.
  • the present invention is implemented by the embodiment having the following configuration in order to achieve the above object.
  • the method for purifying thinner waste liquid according to the present invention comprises distilling and recovering the distillate from which the high boiling point impurities having a higher boiling point than the thinner waste liquid are distilled into the reactor. ; A high boiling point material removing step of removing the high boiling point impurities remaining in the reactor after the recovering step; A low boiling point material removing step of distilling the distillate into a reactor and distilling a low boiling point impurity having a lower boiling point than a compound for thinner; And a step of obtaining a thinner composition by recovering the residue remaining in the reactor after the low boiling point material removing step.
  • the method for purifying thinner waste liquid according to the present invention further includes an azeotrope forming step in which an azeotrope is formed in the thinner waste liquid, and the thinner waste liquid in the recovery step is a thinner in which the azeotrope is formed.
  • the waste solution is used, and the high boiling point impurity includes any one or more of a compound having a higher boiling point than the compound for thinner and an azeotrope having a higher boiling point than the compound for thinner, and the low boiling point impurity has a lower boiling point than the compound for thinner. It is characterized in that it comprises any one or more of the compound and azeotrope having a lower boiling point than the compound for thinner.
  • the thinner waste liquid is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester, ethyl lactate, and the like. It is characterized by containing an impurity.
  • the step of removing the high boiling point material comprises an epi removal step of removing ethyl-3-ethoxy propionate. do.
  • the thinner waste liquid according to the present invention is characterized in that the waste liquid of the thinner used in the rinsing process for cleaning the photoresist during the semiconductor manufacturing process is used.
  • the thinner composition obtained in the obtaining step in the method for purifying thinner waste liquid according to the present invention is characterized in that it is used in a rinsing process for cleaning the photoresist during the display manufacturing process.
  • the thinner compound in the method for purifying thinner waste liquid according to the present invention, is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate. Characterized in that it comprises a.
  • the liquid residue remaining in the reactor is recovered, or the residue is distilled off to recover and cooled, It is characterized by obtaining the said thinner composition.
  • the distillate in the recovery step is recovered from when it reaches 135 ° C and is recovered until it reaches 157 ° C, the low boiling point material
  • the low boiling impurity is characterized in that the removal starts from 73 °C until the removal to 145 °C.
  • the distillate in the recovery step is recovered from when it reaches 132 ° C and is recovered until it reaches 160 ° C, the low boiling point material
  • the low boiling point impurity is characterized in that the removal starts from 73 °C until 142 °C to be removed.
  • the thinner composition according to the present invention is characterized in that it is obtained from the purification method of any one of claims 1 to 10.
  • the thinner composition according to the present invention is characterized in that it comprises 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate.
  • the thinner composition according to the present invention is characterized in that it is used in the rinsing process for cleaning the photoresist during the display manufacturing process.
  • the thinner composition according to the invention is obtained from the purification method of claim 9, 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl It comprises 8 to 10 parts by weight of ester and 16 to 20 parts by weight of ethyl lactate.
  • the thinner composition according to the invention is obtained from the purification method of claim 10, 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl It characterized in that it comprises 23 to 30 parts by weight of ester and 12 to 16 parts by weight of ethyl lactate.
  • the method for purifying thinner waste liquid according to the present invention comprises: a low boiling point impurity removal step of distilling low boiling point impurities having a lower boiling point than a compound for thinner by distilling the thinner waste solution into a reactor; A residue recovery step of recovering the residue remaining in the reactor after the low boiling point impurities removal step; Distilling the residue from the reactor to obtain a thinner composition by distilling a distillate from which a high boiling point impurity having a higher boiling point is removed than a compound for thinner; It characterized in that it comprises a high boiling point impurities removal step of removing the high boiling point impurities remaining in the reactor after the composition obtaining step.
  • the method for purifying thinner waste liquid according to the present invention further includes an azeotrope forming step in which an azeotrope is formed in the thinner waste liquid, wherein the thinner waste liquid in the low boiling point impurities removal step is an azeotrope.
  • the formed thinner waste liquid is used, and the low boiling point impurity includes any one or more of a compound having a lower boiling point than the compound for thinner and an azeotrope having a lower boiling point than the compound for thinner, wherein the high boiling point impurity is higher than the compound for thinner It characterized in that it comprises any one or more of a compound having a point and azeotropes having a higher boiling point than the compound for thinner.
  • the thinner waste liquid is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester, ethyl lactate, and the like. It is characterized by containing an impurity.
  • the high boiling point impurity removing step includes an IP removal step of removing ethyl-3-ethoxy propionate. do.
  • the thinner waste liquid according to the present invention is characterized in that the waste liquid of the thinner used in the rinsing process for cleaning the photoresist during the semiconductor manufacturing process is used.
  • the thinner composition obtained in the composition obtaining step is used in a rinsing process for cleaning a photoresist during display manufacturing. .
  • the thinner compound in the method for purifying thinner waste liquid according to the present invention, is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate. Characterized in that it comprises a.
  • the thinner composition according to the invention is characterized in that it is obtained from the purification method of any one of claims 16 to 22.
  • the thinner composition according to the present invention is characterized in that it comprises 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate.
  • the thinner composition according to the invention is characterized in that it is used in the rinsing process for cleaning the photoresist during the display manufacturing process.
  • the thinner composition according to the present invention is 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 8 to 10 parts by weight of 2-hydroxyisobutyric acid methyl ester and ethyl lac It characterized in that it comprises 16 to 20 parts by weight of tate.
  • the thinner composition according to the present invention is 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 23 to 30 parts by weight of 2-hydroxyisobutyric acid methyl ester and ethyl lac And 12 to 16 parts by weight of tate.
  • the present invention can achieve the following effects by the above embodiment.
  • the present invention has the effect of obtaining a thinner composition that can be used in the rinsing process of the display manufacturing process using the waste solution of the thinner used in the rinsing process of cleaning the photoresist during the semiconductor manufacturing process.
  • the present invention has the effect of improving the economic efficiency by using the purified product directly as a thinner composition without adding a specific compound or using a specific device other than distillation to remove impurities.
  • 1 is a photograph of a specimen coated with a photoresist.
  • Figure 2 is a photograph of the specimen treated with the thinner composition according to the embodiments of the present invention.
  • an azeotropic mixture formation step in which an azeotrope is formed in the thinner waste liquid and distilling the thinner waste liquid into a reactor to remove high boiling point impurities having a higher boiling point than the thinner compound
  • a recovery step of distilling the distillate A high boiling point material removing step of removing the high boiling point impurities remaining in the reactor after the recovering step;
  • a step of obtaining a thinner composition by recovering the residue remaining in the reactor after the low boiling point material removing step.
  • the azeotropic mixture forming step is a step in which an azeotrope is formed in the thinner waste liquid, and the thinner waste liquid is the waste liquid of the thinner used in the rinsing process for cleaning the photoresist during the semiconductor manufacturing process (hereinafter referred to as 'the waste of the thinner for semiconductor' Is preferably used.
  • the waste liquid of the thinner for semiconductor various compounds such as thinner component, photoresist component and other impurities are mixed, some of which may form an azeotrope.
  • the boiling point of the azeotrope is different from the boiling point of each compound that forms the azeotrope (eg, water (boiling at 100 ° C.) and N-butyl acetate (127 ° C.) contained in the waste liquid of the thinner for semiconductors). Boiling) forms an azeotrope and the boiling point is changed to 85 to 95 °C), that is, the break point of the azeotrope is lower or higher than the boiling point of each compound constituting the azeotrope, the present invention recovers in consideration of this Step and low boiling point material removal step are performed.
  • each compound that forms the azeotrope eg, water (boiling at 100 ° C.) and N-butyl acetate (127 ° C.) contained in the waste liquid of the thinner for semiconductors.
  • Boiling forms an azeotrope and the boiling point is changed to 85 to 95 °C), that is, the break point of the azeotrope is lower or higher than the boiling point
  • the waste liquid of the thinner for semiconductors is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester, ethyl lactate. Ethyl lactate, 1-methoxy-2-propanol, N-butyl acetate, cyclohexanone, gamma-butyrolactone, Iso-propanol, ethyl-3-ethoxy propionate, water, and the like.
  • the purified product obtained by simple distillation of the waste liquid of the semiconductor thinner cannot be used as a semiconductor thinner (in order to purify the waste liquid of the semiconductor thinner and use it again as a semiconductor thinner, a specific compound may be further mixed to provide specific impurities).
  • the present invention is simple without adding a specific compound or using a specific device other than distillation to remove impurities from the waste liquid of the semiconductor thinner,
  • the purified product obtained through the distillation process can be used as a thinner (hereinafter, referred to as a 'display thinner') used in the rinsing process to clean the photoresist during the display manufacturing process, thereby improving economic efficiency.
  • a 'display thinner' used in the rinsing process to clean the photoresist during the display manufacturing process, thereby improving economic efficiency.
  • the compound serves to clean the photoresist (hereinafter, referred to as a 'thinner compound', and the thinner compound is referred to as 1-methoxy-.
  • the compound to be removed includes ethyl-3-ethoxy propionate and water), and a compound which is included in the display thinner and does not significantly affect the cleaning power of the thinner (hereinafter referred to as a 'neutral compound').
  • the purifying method of the present invention has been completed so that the compound for removal can be sufficiently removed and the thinner compound can be obtained at a predetermined ratio so that the purified product has an effective cleaning power. Accordingly, a certain amount (within 6%) of the neutral compound may be included in the purified product, but this does not affect thinner cleaning power, and the process for allowing the neutral compound to be sufficiently removed is not included in the purification method, thereby further improving the economics of the present invention. It can be improved.
  • the recovering step is a step of distilling the distillate from which the high-boiling impurities having a higher boiling point than the compound for thinner are removed by distilling the thinner waste solution into the reactor.
  • the impurity means a compound other than the compound for thinner among the compounds contained in the thinner waste solution.
  • the thinner waste liquid may be a thinner waste liquid in which an azeotrope is formed, and the reactor may use various conventional apparatuses such as a distillator used to separate a liquid mixture, and the compound for thinner is 1-methoxy-2-.
  • the distillate is preferably recovered from when it reaches 135 ° C until it reaches 157 ° C.
  • the thinner waste liquid is placed in a still (not shown) and continuously heated to form a distillate, which is installed at the top of the distiller when the temperature of the thermometer located at the top of the still, that is, the temperature of the distillate, reaches 135 ° C.
  • the valve is opened to start the recovery of the distillate out of the reactor and when the temperature exceeds 157 ° C., the valve is closed to recover the distillate until the temperature of the distillate reaches 157 ° C.
  • the high boiling point material removing step is to remove the high boiling point impurities remaining in the reactor after the recovery step, an IP removal step of removing ethyl-3-ethoxy propionate, and ethyl-3-ethoxy pro And other high boiling impurity removal steps to remove high boiling point impurities other than cypionate.
  • the EPI removal step and the other high boiling point impurity removal step may be performed separately or simultaneously. Since the high boiling point impurities such as ethyl-3-ethoxy propionate, which have not been distilled, remain in the reactor after the recovery step, the high boiling point material removing step removes the high boiling point impurities from the reactor.
  • the low boiling point material removing step is distilling the low boiling point impurities having a lower boiling point than the thinner compound by distilling the distillate into the reactor.
  • the low boiling point impurity includes any one or more of a compound having a lower boiling point than the compound for thinner and an azeotrope having a lower boiling point than the compound for thinner, and the low boiling point impurities are removed from the low boiling point material removal step at 73 ° C. It is preferable to remove until it becomes 145 degreeC.
  • the low boiling point material removing step is to put the distillate (liquid state) recovered in the recovery step into a still (not shown) and continuously heated to form a new distillate (low boiling point impurities in the gaseous state) and the temperature of the new distillate is Starting at 73 ° C., the valve is opened to start removing fresh distillate out of the reactor. When the temperature is above 145 ° C., the valve is closed to remove fresh distillate until the temperature of the new distillate is 145 ° C.
  • the obtaining step is to recover the residue remaining in the reactor after the low boiling point material removal step to obtain a thinner composition, in the obtaining step to recover the liquid residue remaining in the reactor, or to recover the residue
  • distillation and recovery distillate is recovered from when it reaches 135 ° C and recovered until it reaches 157 ° C
  • the thinner composition is obtained.
  • the thinner compound is contained in an amount of 97 to 99% by weight relative to the total weight of the residue, and the thinner composition is used in a rinsing process for cleaning the photoresist during display manufacturing.
  • the thinner composition (residue) obtained in the obtaining step contains 95 to 98% by weight of the compound for thinner relative to the total weight of the residue
  • the thinner composition is used in the rinsing process for cleaning the photoresist during the display manufacturing process, 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester 23 to 30 parts by weight and 12 to 16 parts by weight of ethyl lactate.
  • a method for purifying thinner waste liquid includes an azeotropic mixture forming step in which an azeotrope is formed in the thinner waste liquid, and a low boiling point for distilling low boiling point impurities having a lower boiling point than the compound for thinner by distilling the thinner waste liquid into a reactor.
  • a high boiling point impurity removal step of removing the high boiling point impurities remaining in the reactor after the composition obtaining step.
  • the thinner waste liquid purifying method according to another embodiment of the present invention has a low boiling point unlike the purification method of the thinner waste liquid according to an embodiment of the present invention, in which a high boiling point impurities are first removed and later, the low boiling point impurities are removed to obtain a thinner composition. Since there is only a difference that the impurities are first removed and later the high boiling point impurities are removed to obtain the thinner composition, detailed descriptions of common parts will be omitted.
  • the low boiling point impurities removal step is a step of distilling out the low boiling point impurities having a lower boiling point than the thinner waste liquid by distilling the reactor.
  • the low boiling point impurity is preferably removed until it reaches 145 ° C from when the removal starts from 73 ° C.
  • the residue recovery step is a step of recovering the residue remaining in the reactor after the low boiling point impurities removal step.
  • the composition obtaining step is to obtain a thinner composition by distilling the residue from the reactor to distill the distillate from which the high boiling point impurities having a higher boiling point than the thinner compound are removed.
  • the distillate is preferably recovered from when it reaches 135 ° C until it reaches 157 ° C.
  • the thinner composition (distillate) obtained in the composition acquisition step will contain 97 to 99% by weight of the thinner compound relative to the total weight of the distillate, and the thinner composition may be used in a rinsing process for cleaning the photoresist during display manufacturing.
  • the high boiling point impurity removing step is to remove the high boiling point impurities remaining in the reactor after the composition obtaining step, an IP removal step of removing ethyl-3-ethoxy propionate, and ethyl-3-ethoxy And other high boiling impurity removal steps to remove high boiling impurity except propionate.
  • the low boiling point material removing step the low boiling point impurity is removed from 73 ° C. until it is removed until 142 ° C., and in the obtaining step of the composition, recovery is started at 160 ° C. when the distillate becomes 132 ° C.
  • the thinner composition (distillate) obtained in the composition obtaining step is a distillation compound for thinner 95 to 98% by weight relative to the total weight of water
  • the thinner composition is used in the rinsing process for cleaning the photoresist during the display manufacturing process, 50-60 parts by weight of 1-methoxy-2-propanol acetate, 2- It will comprise 23 to 30 parts by weight of hydroxyisobutyric acid methyl ester and 12 to 16 parts by weight of ethyl lactate.
  • the thinner composition includes 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate, and is used as waste liquid of thinner used in a rinsing process for cleaning photoresist during semiconductor manufacturing. It is derived from, characterized in that used in the rinse process for cleaning the photoresist during the display manufacturing process.
  • the thinner composition according to another embodiment of the present invention is 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 8 to 10 parts by weight of 2-hydroxyisobutyric acid methyl ester and 16 to 20 parts by weight of ethyl lactate. Contains wealth.
  • Another thinner composition according to another embodiment of the present invention is 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 23 to 30 parts by weight of 2-hydroxyisobutyric acid methyl ester and 12 to 16 parts by weight of ethyl lactate. Contains wealth.
  • Example 1 From the time when the temperature became 137 degreeC in Example 1 (1), collection
  • a thinner composition consisting of 70 parts by weight of 1-methoxy-2-propanol acetate and 30 parts by weight of 1-methoxy-2-propanol was formed.
  • Ethyl-3-ethoxy propionate was further added to the thinner composition obtained in Example 1, 70.5 parts by weight of 1-methoxy-2-propanol acetate, 9.1 parts by weight of 2-hydroxyisobutyric acid methyl ester, A thinner composition was formed consisting of 18 parts by weight of ethyl lactate, 2.16 parts by weight of ethyl-3-ethoxy propionate, 0.01 part by weight of water, and 2.39 parts by weight of other impurities.
  • Example 2 To the thinner composition obtained in Example 1, water was further added, and 70.5 parts by weight of 1-methoxy-2-propanol acetate, 9.1 parts by weight of 2-hydroxyisobutyric acid methyl ester, 18 parts by weight of ethyl lactate, and ethyl- A thinner composition consisting of 0.16 parts by weight of 3-ethoxy propionate, 1.01 part by weight of water and 2.39 parts by weight of other impurities was formed.
  • a thinner composition consisting of 40 parts by weight of 1-methoxy-2-propanol acetate, 30 parts by weight of 2-hydroxyisobutyric acid methyl ester, and 30 parts by weight of ethyl lactate was formed.
  • a commercially available photoresist used in a display manufacturing process was applied to a slide glass, and soft baking was performed for 1 hour in an oven at 80 ° C. to prepare a specimen as shown in FIG. 1.
  • the thinner compositions (50 ml) of Examples 1 and 2 and Comparative Examples 1 to 5 were placed in a 100 ml beaker, the beaker was placed in an ultrasonic cleaner, and the sample was completely immersed in the beaker, and then the ultrasonic cleaner was operated.
  • Comparative Examples 2, 3 and 5 can be seen that the photoresist cleaning power is lower than 1 in comparison, through this, ethyl-3-ethoxy propionate, water is deteriorating the cleaning power, 1-methoxy-2-propanol Even if it consists of acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate, it can be seen that it does not serve as a display thinner unless mixed in a specific ratio.
  • Example 1 Example 2 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Cleaning power compared to Comparative Example 1 good good Bad Bad good Bad

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Abstract

The present invention relates to a method for purifying a waste solution of a thinner and, more specifically, to a method for purifying a waste solution of thinner, by which a waste solution of a thinner used in a rinse process for cleaning a photoresist in a semiconductor fabrication process can be used in a rinse process of a display manufacturing process. Without adding a specific compound or using specific equipment other than for distillation in order to remove impurities, a purified product can be immediately used as a thinner composition without the addition of a specific ingredient, and thus economic efficiency can be improved.

Description

신너 폐액의 정제방법 및 그로부터 수득되는 신너 조성물Method for purifying thinner waste liquid and thinner composition obtained therefrom

본 발명은 신너 폐액의 정제방법에 대한 것으로, 더욱 상세하게는 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액을 이용하여 디스플레이 제조과정의 린스공정에서 사용할 수 있으며, 불순물을 제거하기 위해 특정 화합물을 첨가하거나 증류외 특정 장치를 이용하지 않고, 특정 성분의 추가 없이 정제물을 바로 신너 조성물로 이용하여 경제성을 향상시킬 수 있는 신너 폐액의 정제방법에 대한 것이다.The present invention relates to a method for purifying thinner waste liquid, and more particularly, it can be used in the rinsing process of the display manufacturing process using the waste liquid of the thinner used in the rinsing process of cleaning the photoresist during the semiconductor manufacturing process, and removes impurities. The present invention relates to a method for purifying thinner waste liquid which can improve economic efficiency by using a purified product directly as a thinner composition without adding a specific compound or using a specific device other than distillation.

포토레지스트 세정용 신너는 반도체 또는 디스플레이 제조과정에서 노광 및 식각 공정을 진행한 이후 남아있는 포토레지스트(Photoresist)를 세정하기 위한 린스공정에서 사용되는데, 상기 신너는 특정 화학물질이 특정 성분비로 혼합되어 다양하게 제조되나, 디스플레이 제조과정의 린스공정에서는 대표적으로 1-메톡시-2-프로판올아세테이트 70중량%와 1-메톡시-2-프로판올 30중량%로 이루어진 신너가 사용된다. 상기 린스공정에서 사용된 신너의 폐액을 폐기하는 경우 환경을 오염시키고 비경제적인 문제가 있어, 하기의 특허문헌처럼 증류 등을 이용하는 방법에 의해 상기 신너 폐액에 포함되어 있는 신너 성분을 회수하여 재활용하고 있다.The photoresist cleaning thinner is used in a rinsing process for cleaning the remaining photoresist after exposure and etching in semiconductor or display manufacturing process. The thinner is mixed with specific chemicals in a specific component ratio. However, in the rinsing process of the display manufacturing process, a thinner consisting of 70% by weight of 1-methoxy-2-propanol acetate and 30% by weight of 1-methoxy-2-propanol is typically used. When the waste liquid of the thinner used in the rinsing process is disposed, there is a problem of polluting the environment and uneconomical, and the thinner component contained in the thinner waste liquid is recovered and recycled by using distillation or the like as the following patent document. .

(특허문헌)(Patent literature)

공개특허공보 제10-2016-0012721호(2016. 02. 03. 공개) "포토레지스트 린스용 신너 폐액의 정제방법"Publication No. 10-2016-0012721 (published Feb. 03, 2016) "Method for Purifying Thinner Waste for Photoresist Rinse"

하지만, 종래의 신너 폐액의 정제방법은 신너 폐액에 들어있는 불순물을 제거하기 위해 알칼리 화합물, 벤조일클로라이드 등의 화합물을 추가로 첨가하거나, 증류 과정 외에 분리기를 이용하여 별도로 불순물을 제거하여야 하는 문제가 있다. 또한, 종래의 신너 폐액의 정제방법에 의해 얻은 물질을 바로 신너로 이용할 수 없어, 특정 성분을 추가로 혼합하여야 하는 문제가 있었다.However, the conventional method for purifying thinner waste liquid has a problem in that an additional compound such as an alkali compound, benzoyl chloride, etc. is added to remove impurities in the thinner waste liquid, or impurities are separately removed using a separator in addition to the distillation process. . In addition, the substance obtained by the conventional thinner waste liquid purification method cannot be used directly as a thinner, and there is a problem in that specific components must be further mixed.

본 발명은 상기의 문제점을 해결하기 위해 안출된 것으로,The present invention has been made to solve the above problems,

본 발명은 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액을 이용하여 디스플레이 제조과정의 린스공정에서 사용할 수 있는 신너 조성물을 수득할 수 있는 신너 폐액의 정제방법을 제공하는데 그 목적이 있다.The present invention provides a method for purifying thinner waste liquid which can obtain a thinner composition which can be used in the rinse process of the display manufacturing process by using the waste liquid used in the rinse process for cleaning the photoresist during the semiconductor manufacturing process. There is this.

또한, 본 발명은 불순물을 제거하기 위해 특정 화합물을 첨가하거나 증류외 특정 장치를 이용하지 않고, 특정 성분의 추가 없이 정제물을 바로 신너 조성물로 이용하여 경제성을 향상시킬 수 있는 신너 폐액의 정제방법을 제공하는데 그 목적이 있다.In addition, the present invention provides a method for purifying thinner waste liquid which can improve economic efficiency by using a purified product directly as a thinner composition without adding a specific compound or using a specific device other than distillation to remove impurities. The purpose is to provide.

본 발명은 앞서 본 목적을 달성하기 위하여 다음과 같은 구성을 가진 실시예에 의해 구현된다.The present invention is implemented by the embodiment having the following configuration in order to achieve the above object.

본 발명의 일 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법은 신너 폐액을 반응기에 넣고 증류하여 신너용 화합물보다 고비점을 가지는 고비점불순물이 제거된 증류물을 증류회수하는 회수단계와; 상기 회수단계 후 상기 반응기에 잔류한 고비점불순물을 제거하는 고비점물질제거단계와; 상기 증류물을 반응기에 넣고 증류하여 신너용 화합물보다 저비점을 가지는 저비점불순물을 증류제거하는 저비점물질제거단계와; 상기 저비점물질제거단계 후 상기 반응기에 잔류하는 잔류물을 회수하여 신너 조성물을 수득하는 수득단계;를 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the method for purifying thinner waste liquid according to the present invention comprises distilling and recovering the distillate from which the high boiling point impurities having a higher boiling point than the thinner waste liquid are distilled into the reactor. ; A high boiling point material removing step of removing the high boiling point impurities remaining in the reactor after the recovering step; A low boiling point material removing step of distilling the distillate into a reactor and distilling a low boiling point impurity having a lower boiling point than a compound for thinner; And a step of obtaining a thinner composition by recovering the residue remaining in the reactor after the low boiling point material removing step.

본 발명의 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법은 신너 폐액에서 공비혼합물이 형성되는 공비혼합물형성단계를 추가로 포함하며, 상기 회수단계에서 상기 신너 폐액은 공비혼합물이 형성된 신너 폐액이 사용되고, 상기 고비점불순물은 상기 신너용 화합물보다 고비점을 가지는 화합물 및 상기 신너용 화합물보다 고비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하며, 상기 저비점불순물은 상기 신너용 화합물보다 저비점을 가지는 화합물 및 상기 신너용 화합물보다 저비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하는 것을 특징을 한다.According to another embodiment of the present invention, the method for purifying thinner waste liquid according to the present invention further includes an azeotrope forming step in which an azeotrope is formed in the thinner waste liquid, and the thinner waste liquid in the recovery step is a thinner in which the azeotrope is formed. The waste solution is used, and the high boiling point impurity includes any one or more of a compound having a higher boiling point than the compound for thinner and an azeotrope having a higher boiling point than the compound for thinner, and the low boiling point impurity has a lower boiling point than the compound for thinner. It is characterized in that it comprises any one or more of the compound and azeotrope having a lower boiling point than the compound for thinner.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 신너 폐액은 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터, 에틸락테이트 및 불순물을 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, in the method for purifying thinner waste liquid according to the present invention, the thinner waste liquid is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester, ethyl lactate, and the like. It is characterized by containing an impurity.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 고비점물질제거단계는 에틸-3-에톡시 프로피오네이트를 제거하는 이이피제거단계를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, in the method for purifying thinner waste liquid according to the present invention, the step of removing the high boiling point material comprises an epi removal step of removing ethyl-3-ethoxy propionate. do.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 신너 폐액은 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액이 이용되는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner waste liquid according to the present invention is characterized in that the waste liquid of the thinner used in the rinsing process for cleaning the photoresist during the semiconductor manufacturing process is used.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 수득단계에서 수득되는 상기 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner composition obtained in the obtaining step in the method for purifying thinner waste liquid according to the present invention is characterized in that it is used in a rinsing process for cleaning the photoresist during the display manufacturing process.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 신너용 화합물은 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, in the method for purifying thinner waste liquid according to the present invention, the thinner compound is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate. Characterized in that it comprises a.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 수득단계에서는 반응기에 잔류하는 액체 상태의 잔류물을 회수하거나, 상기 잔류물을 다시 증류하여 회수하고 냉각하여, 상기 신너 조성물을 얻는 것을 특징으로 한다.According to another embodiment of the present invention, in the method for purifying thinner waste liquid according to the present invention, in the obtaining step, the liquid residue remaining in the reactor is recovered, or the residue is distilled off to recover and cooled, It is characterized by obtaining the said thinner composition.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 회수단계에서 증류물은 135℃가 될 때부터 회수가 시작되어 157℃가 될 때까지 회수되며, 상기 저비점물질제거단계에서 저비점불순물은 73℃가 될 때부터 제거가 시작되어 145℃가 될 때까지 제거되는 것을 특징으로 한다.According to another embodiment of the present invention, in the refining method of the thinner waste liquid according to the present invention, the distillate in the recovery step is recovered from when it reaches 135 ° C and is recovered until it reaches 157 ° C, the low boiling point material In the removing step, the low boiling impurity is characterized in that the removal starts from 73 ℃ until the removal to 145 ℃.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 회수단계에서 증류물은 132℃가 될 때부터 회수가 시작되어 160℃가 될 때까지 회수되며, 상기 저비점물질제거단계에서 저비점불순물은 73℃가 될 때부터 제거가 시작되어 142℃가 될 때까지 제거되는 것을 특징으로 한다.According to another embodiment of the present invention, in the refining method of the thinner waste liquid according to the present invention, the distillate in the recovery step is recovered from when it reaches 132 ° C and is recovered until it reaches 160 ° C, the low boiling point material In the removal step, the low boiling point impurity is characterized in that the removal starts from 73 ℃ until 142 ℃ to be removed.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 제1항 내지 제10항 중 어느 한 항의 정제방법으로부터 수득되는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner composition according to the present invention is characterized in that it is obtained from the purification method of any one of claims 1 to 10.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner composition according to the present invention is characterized in that it comprises 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner composition according to the present invention is characterized in that it is used in the rinsing process for cleaning the photoresist during the display manufacturing process.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 제9항의 정제방법으로부터 수득되며, 1-메톡시-2-프로판올아세테이트 65 내지 75중량부, 2-하이드록시이소부티릭엑시드메틸에스터 8 내지 10중량부 및 에틸락테이트 16 내지 20중량부를 포함하는 것을 특징으로 한다.According to another embodiment of the invention, the thinner composition according to the invention is obtained from the purification method of claim 9, 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl It comprises 8 to 10 parts by weight of ester and 16 to 20 parts by weight of ethyl lactate.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 제10항의 정제방법으로부터 수득되며, 1-메톡시-2-프로판올아세테이트 50 내지 60중량부, 2-하이드록시이소부티릭엑시드메틸에스터 23 내지 30중량부 및 에틸락테이트 12 내지 16중량부를 포함하는 것을 특징으로 한다.According to another embodiment of the invention, the thinner composition according to the invention is obtained from the purification method of claim 10, 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl It characterized in that it comprises 23 to 30 parts by weight of ester and 12 to 16 parts by weight of ethyl lactate.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법은 신너 폐액을 반응기에 넣고 증류하여 신너용 화합물보다 저비점을 가지는 저비점불순물을 증류제거하는 저비점불순물제거단계와; 상기 저비점불순물제거단계 후 상기 반응기에 잔류하는 잔류물을 회수하는 잔류물회수단계와; 상기 잔류물을 반응기에서 증류하여 신너용 화합물보다 고비점을 가지는 고비점불순물이 제거된 증류물을 증류회수하여 신너 조성물을 수득하는 조성물수득단계와; 상기 조성물수득단계 후 상기 반응기에 잔류한 고비점불순물을 제거하는 고비점불순물제거단계를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, the method for purifying thinner waste liquid according to the present invention comprises: a low boiling point impurity removal step of distilling low boiling point impurities having a lower boiling point than a compound for thinner by distilling the thinner waste solution into a reactor; A residue recovery step of recovering the residue remaining in the reactor after the low boiling point impurities removal step; Distilling the residue from the reactor to obtain a thinner composition by distilling a distillate from which a high boiling point impurity having a higher boiling point is removed than a compound for thinner; It characterized in that it comprises a high boiling point impurities removal step of removing the high boiling point impurities remaining in the reactor after the composition obtaining step.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법은 신너 폐액에서 공비혼합물이 형성되는 공비혼합물형성단계를 추가로 포함하며, 상기 저비점불순물제거단계에서 상기 신너 폐액은 공비혼합물이 형성된 신너 폐액이 사용되고, 상기 저비점불순물은 상기 신너용 화합물보다 저비점을 가지는 화합물 및 상기 신너용 화합물보다 저비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하며, 상기 고비점불순물은 상기 신너용 화합물보다 고비점을 가지는 화합물 및 상기 신너용 화합물보다 고비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하는 것을 특징을 한다.According to another embodiment of the present invention, the method for purifying thinner waste liquid according to the present invention further includes an azeotrope forming step in which an azeotrope is formed in the thinner waste liquid, wherein the thinner waste liquid in the low boiling point impurities removal step is an azeotrope. The formed thinner waste liquid is used, and the low boiling point impurity includes any one or more of a compound having a lower boiling point than the compound for thinner and an azeotrope having a lower boiling point than the compound for thinner, wherein the high boiling point impurity is higher than the compound for thinner It characterized in that it comprises any one or more of a compound having a point and azeotropes having a higher boiling point than the compound for thinner.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 신너 폐액은 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터, 에틸락테이트 및 불순물을 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, in the method for purifying thinner waste liquid according to the present invention, the thinner waste liquid is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester, ethyl lactate, and the like. It is characterized by containing an impurity.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 고비점불순물제거단계는 에틸-3-에톡시 프로피오네이트를 제거하는 이이피제거단계를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, in the purification method of the thinner waste liquid according to the present invention, the high boiling point impurity removing step includes an IP removal step of removing ethyl-3-ethoxy propionate. do.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 신너 폐액은 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액이 이용되는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner waste liquid according to the present invention is characterized in that the waste liquid of the thinner used in the rinsing process for cleaning the photoresist during the semiconductor manufacturing process is used.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 조성물수득단계에서 수득되는 상기 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되는 것을 특징으로 한다.According to another embodiment of the present invention, in the purification method of the thinner waste solution according to the present invention, the thinner composition obtained in the composition obtaining step is used in a rinsing process for cleaning a photoresist during display manufacturing. .

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 폐액의 정제방법에 있어서 상기 신너용 화합물은 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, in the method for purifying thinner waste liquid according to the present invention, the thinner compound is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate. Characterized in that it comprises a.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 제16항 내지 제22항 중 어느 한 항의 정제방법으로부터 수득되는 것을 특징으로 한다.According to another embodiment of the invention, the thinner composition according to the invention is characterized in that it is obtained from the purification method of any one of claims 16 to 22.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner composition according to the present invention is characterized in that it comprises 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 디스플레이 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용되는 것을 특징으로 한다.According to another embodiment of the invention, the thinner composition according to the invention is characterized in that it is used in the rinsing process for cleaning the photoresist during the display manufacturing process.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 1-메톡시-2-프로판올아세테이트 65 내지 75중량부, 2-하이드록시이소부티릭엑시드메틸에스터 8 내지 10중량부 및 에틸락테이트 16 내지 20중량부를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner composition according to the present invention is 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 8 to 10 parts by weight of 2-hydroxyisobutyric acid methyl ester and ethyl lac It characterized in that it comprises 16 to 20 parts by weight of tate.

본 발명의 또 다른 실시예에 따르면, 본 발명에 따른 신너 조성물은 1-메톡시-2-프로판올아세테이트 50 내지 60중량부, 2-하이드록시이소부티릭엑시드메틸에스터 23 내지 30중량부 및 에틸락테이트 12 내지 16중량부를 포함하는 것을 특징으로 한다.According to another embodiment of the present invention, the thinner composition according to the present invention is 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 23 to 30 parts by weight of 2-hydroxyisobutyric acid methyl ester and ethyl lac And 12 to 16 parts by weight of tate.

본 발명은 앞서 본 실시예에 의해 다음과 같은 효과를 얻을 수 있다.The present invention can achieve the following effects by the above embodiment.

본 발명은 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액을 이용하여 디스플레이 제조과정의 린스공정에서 사용할 수 있는 신너 조성물을 수득할 수 있는 효과가 있다.The present invention has the effect of obtaining a thinner composition that can be used in the rinsing process of the display manufacturing process using the waste solution of the thinner used in the rinsing process of cleaning the photoresist during the semiconductor manufacturing process.

또한, 본 발명은 불순물을 제거하기 위해 특정 화합물을 첨가하거나 증류외 특정 장치를 이용하지 않고, 특정 성분의 추가 없이 정제물을 바로 신너 조성물로 이용하여 경제성을 향상시킬 수 있는 효과가 있다.In addition, the present invention has the effect of improving the economic efficiency by using the purified product directly as a thinner composition without adding a specific compound or using a specific device other than distillation to remove impurities.

도 1은 포토레지스트가 도포된 시편 사진.1 is a photograph of a specimen coated with a photoresist.

도 2는 본 발명의 실시예들에 따른 신너 조성물을 처리한 시편의 사진.Figure 2 is a photograph of the specimen treated with the thinner composition according to the embodiments of the present invention.

이하에서는 본 발명에 따른 신너 폐액의 정제방법 및 그로부터 수득되는 신너 조성물을 첨부된 도면을 참조하여 상세히 설명한다. 특별한 정의가 없는 한 본 명세서의 모든 용어는 본 발명이 속하는 기술분야의 통상의 지식을 가진 기술자가 이해하는 당해 용어의 일반적 의미와 동일하고 만약 본 명세서에 사용된 용어의 의미와 충돌하는 경우에는 본 명세서에 사용된 정의에 따른다 명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Hereinafter, a method for purifying thinner waste liquid according to the present invention and a thinner composition obtained therefrom will be described in detail with reference to the accompanying drawings. Unless otherwise defined, all terms in this specification are equivalent to the general meaning of the terms understood by those of ordinary skill in the art to which the present invention pertains, and in case of conflict with the meaning of the terms used herein In accordance with the definitions used in the specification, when a part is said to "include" a certain component, unless otherwise stated, it may include other components rather than exclude other components. it means.

본 발명의 일 실시예에 따른 신너 폐액의 정제방법은 신너 폐액에서 공비혼합물이 형성되는 공비혼합물형성단계와, 신너 폐액을 반응기에 넣고 증류하여 신너용 화합물보다 고비점을 가지는 고비점불순물이 제거된 증류물을 증류회수하는 회수단계와; 상기 회수단계 후 상기 반응기에 잔류한 고비점불순물을 제거하는 고비점물질제거단계와; 상기 증류물을 반응기에 넣고 증류하여 신너용 화합물보다 저비점을 가지는 저비점불순물을 증류제거하는 저비점물질제거단계와; 상기 저비점물질제거단계 후 상기 반응기에 잔류하는 잔류물을 회수하여 신너 조성물을 수득하는 수득단계;를 포함하는 것을 특징으로 한다.In the method for purifying thinner waste liquid according to an embodiment of the present invention, an azeotropic mixture formation step in which an azeotrope is formed in the thinner waste liquid and distilling the thinner waste liquid into a reactor to remove high boiling point impurities having a higher boiling point than the thinner compound A recovery step of distilling the distillate; A high boiling point material removing step of removing the high boiling point impurities remaining in the reactor after the recovering step; A low boiling point material removing step of distilling the distillate into a reactor and distilling a low boiling point impurity having a lower boiling point than a compound for thinner; And a step of obtaining a thinner composition by recovering the residue remaining in the reactor after the low boiling point material removing step.

상기 공비혼합물형성단계는 신너 폐액에서 공비혼합물이 형성되는 단계로, 상기 신너 폐액은 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액(이하, '반도체용 신너의 폐액'이라 함)이 이용되는 것을 바람직하다. 상기 반도체용 신너의 폐액에는 신너 성분, 포토레지스트 성분, 기타 불순물 등의 여러 화합물이 혼합되어 있는데, 이중 일부 화합물들은 공비혼합물을 형성할 수 있다. 상기 공비혼합물이 형성되면, 공비혼합물의 끓는점은 공비혼합물을 이루는 각각의 화합물의 끓는점과 달라져(예컨대, 반도체용 신너의 폐액에 포합되어 있는 물(100℃에서 끓음)과 N-부틸 아세테이트(127℃에서 끓음)는 공비혼합물을 형성하고, 끓는점이 85 내지 95℃로 변화하게 됨), 즉 공비혼합물의 끊는점이 공비혼합물을 이루는 각각의 화합물의 끓는점보다 낮아지거나 높아지게 되므로, 본원발명은 이를 고려하여 회수단계 및 저비점물질제거단계가 수행되게 된다. 상기 반도체용 신너의 폐액은 1-메톡시-2-프로판올아세테이트(1-methoxy-2-propanol acetate), 2-하이드록시이소부티릭엑시드메틸에스터(2-hydoxyisobutyric acid methyl ester), 에틸락테이트(Ethyl lactate), 1-메톡시-2-프로판올(1-methoxy-2-propanol), N-부틸 아세테이트(N-butyl acetate), 사이클로헥사논(Cyclohexanone), 감마부티로락톤(Gamma-butyrolactone), 이소프로판올(Iso-propanol), 에틸-3-에톡시 프로피오네이트(Ethyl-3-ethoxy propionate), 물 등을 포함할 수 있다. 상기 반도체용 신너의 폐액을 단순 증류하여 얻은 정제물은 반도체용 신너로 이용할 수 없는바(상기 반도체용 신너의 폐액을 정제하여 다시 반도체용 신너로 이용하기 위해서는 특정 화합물을 추가로 혼합하여 특정 불순물을 제거하거나 정제물에 특정 성분을 추가로 혼합하여야 함), 본원발명은 상기 반도체용 신너의 폐액에서 불순물을 제거하기 위해 특정 화합물을 첨가하거나 증류외 특정 장치를 이용하지 않고, 특정 성분의 추가 없이 단순 증류과정을 통해 얻은 정제물을 바로 디스플레이 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용되는 신너(이하, '디스플레이용 신너'라 함)로 이용하여 경제성을 향상시킬 수 있게 된다. 이를 위해, 상기 반도체용 신너의 폐액에는 일정 비율로 디스플레이용 신너에 포함되면 포토레지스트를 세정하는 역할을 수행하는 화합물(이하, '신너용 화합물'이라 하고, 상기 신너용 화합물에는 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트가 있음), 소량이라도 디스플레이용 신너에 포함되면 신너의 세정력을 떨어뜨리는 화합물(이하, '제거요구 화합물'이라 하고, 상기 제거요구 화합물에는 에틸-3-에톡시 프로피오네이트 및 수분이 있음), 디스플레용 신너에 포함되어도 신너의 세정력에는 큰 영향을 끼지지 않는 화합물(이하, '중립 화합물'이라 하고, 상기 중립화합물은 1-메톡시-2-프로판올, N-부틸 아세테이트, 사이클로헥사논, 감마부티로락톤 및 이소프로판올이 있음)이 포함되어 있음을 알아 내어, 제거요구 화합물은 충분히 제거될 수 있고, 정제물이 효과적인 세정력을 가지도록 신너용 화합물이 일정 비율로 수득될 수 있도록 하는 본원발명의 정제방법이 완성되었다. 이에 따라, 일정량(6% 이내)의 중립 화합물이 정제물에 포함될 수 있으나, 이는 신너 세정력에 영향을 미치지 않으며, 중립 화합물이 충분히 제거되도록 하는 공정이 정제방법에 포함되지 않아 본원발명의 경제성을 더욱 향상시킬 수 있게 된다.The azeotropic mixture forming step is a step in which an azeotrope is formed in the thinner waste liquid, and the thinner waste liquid is the waste liquid of the thinner used in the rinsing process for cleaning the photoresist during the semiconductor manufacturing process (hereinafter referred to as 'the waste of the thinner for semiconductor' Is preferably used. In the waste liquid of the thinner for semiconductor, various compounds such as thinner component, photoresist component and other impurities are mixed, some of which may form an azeotrope. When the azeotrope is formed, the boiling point of the azeotrope is different from the boiling point of each compound that forms the azeotrope (eg, water (boiling at 100 ° C.) and N-butyl acetate (127 ° C.) contained in the waste liquid of the thinner for semiconductors). Boiling) forms an azeotrope and the boiling point is changed to 85 to 95 ℃), that is, the break point of the azeotrope is lower or higher than the boiling point of each compound constituting the azeotrope, the present invention recovers in consideration of this Step and low boiling point material removal step are performed. The waste liquid of the thinner for semiconductors is 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester, ethyl lactate. Ethyl lactate, 1-methoxy-2-propanol, N-butyl acetate, cyclohexanone, gamma-butyrolactone, Iso-propanol, ethyl-3-ethoxy propionate, water, and the like. The purified product obtained by simple distillation of the waste liquid of the semiconductor thinner cannot be used as a semiconductor thinner (in order to purify the waste liquid of the semiconductor thinner and use it again as a semiconductor thinner, a specific compound may be further mixed to provide specific impurities). Must be removed or additionally mixed with a specific component in the purified product), the present invention is simple without adding a specific compound or using a specific device other than distillation to remove impurities from the waste liquid of the semiconductor thinner, The purified product obtained through the distillation process can be used as a thinner (hereinafter, referred to as a 'display thinner') used in the rinsing process to clean the photoresist during the display manufacturing process, thereby improving economic efficiency. To this end, when the waste liquid of the semiconductor thinner is included in the display thinner at a predetermined ratio, the compound serves to clean the photoresist (hereinafter, referred to as a 'thinner compound', and the thinner compound is referred to as 1-methoxy-. 2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate), a compound that reduces the cleaning ability of the thinner when contained in the display thinner even in small amounts (hereinafter referred to as a 'removal compound' The compound to be removed includes ethyl-3-ethoxy propionate and water), and a compound which is included in the display thinner and does not significantly affect the cleaning power of the thinner (hereinafter referred to as a 'neutral compound'). 1-methoxy-2-propanol, N-butyl acetate, cyclohexanone, gamma butyrolactone and isopropanol) The purifying method of the present invention has been completed so that the compound for removal can be sufficiently removed and the thinner compound can be obtained at a predetermined ratio so that the purified product has an effective cleaning power. Accordingly, a certain amount (within 6%) of the neutral compound may be included in the purified product, but this does not affect thinner cleaning power, and the process for allowing the neutral compound to be sufficiently removed is not included in the purification method, thereby further improving the economics of the present invention. It can be improved.

상기 회수단계는 신너 폐액을 반응기에 넣고 증류하여 신너용 화합물보다 고비점을 가지는 고비점 불순물이 제거된 증류물을 증류회수하는 단계이다. 상기 불순물은 신너 폐액에 포합되어 있는 화합물 중 신너용 화합물을 제외한 화합물을 의미한다. 상기 신너 폐액은 공비혼합물이 형성된 신너 폐액이 사용될 수 있으며, 상기 반응기는 액체 혼합물을 분리하기 위해 사용하는 증류기 등의 종래의 다양한 장치가 사용될 수 있고, 상기 신너용 화합물은 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하며, 상기 고비점불순물은 상기 신너용 화합물보다 고비점을 가지는 화합물 및 상기 신너용 화합물보다 고비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하고, 상기 회수단계에서 증류물은 135℃가 될 때부터 회수가 시작되어 157℃가 될 때까지 회수되는 것이 바람직하다. 예컨대, 상기 회수단계는 신너 폐액을 증류기(미도시)에 넣고 계속적으로 가열하여 증류물을 형성하고 증류기 내부 상단에 위치한 온도계의 온도, 즉 증류물의 온도가 135℃가 될 때부터 증류기의 상단에 설치된 밸브를 열어 증류물을 반응기 외부로 회수하는 것을 시작하여 상기 온도가 157℃가 넘으면 밸브를 잠가 증류물의 온도가 157℃될 때까지 증류물을 회수하게 된다.The recovering step is a step of distilling the distillate from which the high-boiling impurities having a higher boiling point than the compound for thinner are removed by distilling the thinner waste solution into the reactor. The impurity means a compound other than the compound for thinner among the compounds contained in the thinner waste solution. The thinner waste liquid may be a thinner waste liquid in which an azeotrope is formed, and the reactor may use various conventional apparatuses such as a distillator used to separate a liquid mixture, and the compound for thinner is 1-methoxy-2-. Propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate, wherein the high boiling point impurity is any of a compound having a higher boiling point than the compound for thinner and an azeotrope having a higher boiling point than the compound for thinner At least one, and in the recovery step, the distillate is preferably recovered from when it reaches 135 ° C until it reaches 157 ° C. For example, in the recovery step, the thinner waste liquid is placed in a still (not shown) and continuously heated to form a distillate, which is installed at the top of the distiller when the temperature of the thermometer located at the top of the still, that is, the temperature of the distillate, reaches 135 ° C. The valve is opened to start the recovery of the distillate out of the reactor and when the temperature exceeds 157 ° C., the valve is closed to recover the distillate until the temperature of the distillate reaches 157 ° C.

상기 고비점물질제거단계는 상기 회수단계 후 상기 반응기에 잔류한 고비점불순물을 제거하는 단계로, 에틸-3-에톡시 프로피오네이트를 제거하는 이이피제거단계와, 에틸-3-에톡시 프로피오네이트를 제외한 고비점불순물을 제거하는 기타고비점불순물제거단계를 포함한다. 상기 이이피제거단계와 기타고비점불순물제거단계는 따로 또는 동시에 진행될 수 있다. 상기 회수단계 후 상기 반응기에는 증류되지 못한 에틸-3-에톡시 프로피오네이트 등의 고비점 불순물이 잔류하므로, 상기 고비점물질제거단계에서는 상기 고비점 불순물을 상기 반응기에서 제거하게 된다.The high boiling point material removing step is to remove the high boiling point impurities remaining in the reactor after the recovery step, an IP removal step of removing ethyl-3-ethoxy propionate, and ethyl-3-ethoxy pro And other high boiling impurity removal steps to remove high boiling point impurities other than cypionate. The EPI removal step and the other high boiling point impurity removal step may be performed separately or simultaneously. Since the high boiling point impurities such as ethyl-3-ethoxy propionate, which have not been distilled, remain in the reactor after the recovery step, the high boiling point material removing step removes the high boiling point impurities from the reactor.

상기 저비점물질제거단계는 증류물을 반응기에 넣고 증류하여 신너용 화합물보다 저비점을 가지는 저비점불순물을 증류제거하는 단계이다. 상기 저비점불순물은 상기 신너용 화합물보다 저비점을 가지는 화합물 및 상기 신너용 화합물보다 저비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하고, 상기 저비점물질제거단계에서 저비점불순물은 73℃가 될 때부터 제거가 시작되어 145℃가 될 때까지 제거되는 것이 바람직하다. 예컨대, 상기 저비점물질제거단계는 상기 회수단계에서 회수된 증류물(액체 상태)을 증류기(미도시)에 넣고 계속적으로 가열하여 새로운 증류물(기상 상태의 저비점불순물)을 형성하고 새로운 증류물의 온도가 73℃가 될 때부터 밸브를 열어 새로운 증류물을 반응기 외부로 제거하는 것을 시작하여 상기 온도가 145℃가 넘으면 밸브를 잠가 새로운 증류물의 온도가 145℃될 때까지 새로운 증류물을 제거하게 된다.The low boiling point material removing step is distilling the low boiling point impurities having a lower boiling point than the thinner compound by distilling the distillate into the reactor. The low boiling point impurity includes any one or more of a compound having a lower boiling point than the compound for thinner and an azeotrope having a lower boiling point than the compound for thinner, and the low boiling point impurities are removed from the low boiling point material removal step at 73 ° C. It is preferable to remove until it becomes 145 degreeC. For example, the low boiling point material removing step is to put the distillate (liquid state) recovered in the recovery step into a still (not shown) and continuously heated to form a new distillate (low boiling point impurities in the gaseous state) and the temperature of the new distillate is Starting at 73 ° C., the valve is opened to start removing fresh distillate out of the reactor. When the temperature is above 145 ° C., the valve is closed to remove fresh distillate until the temperature of the new distillate is 145 ° C.

상기 수득단계는 상기 저비점물질제거단계 후 상기 반응기에 잔류하는 잔류물을 회수하여 신너 조성물을 수득하는 단계로, 상기 수득단계에서는 반응기에 잔류하는 액체 상태의 잔류물을 회수하거나, 상기 잔류물을 다시 증류하고 회수하여(증류물은 135℃가 될 때부터 회수가 시작되어 157℃가 될 때까지 회수됨), 상기 신너 조성물을 얻게 된다. 상기 수득단계에서 수득되는 신너 조성물(잔류물)에는 신너용 화합물이 잔류물의 총중량 대비 97 내지 99중량%로 함유되게 되며, 상기 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되게 되며, 1-메톡시-2-프로판올아세테이트 65 내지 75중량부, 2-하이드록시이소부티릭엑시드메틸에스터 8 내지 10중량부 및 에틸락테이트 16 내지 20중량부를 포함하게 된다. 상기 회수단계에서 증류물이 132℃가 될 때부터 회수가 시작되어 160℃가 될 때까지 회수되고, 상기 저비점물질제거단계에서 저비점불순물이 73℃가 될 때부터 제거가 시작되어 142℃가 될 때까지 제거되는 것을 제외하고, 다른 조건을 상기 신너 폐액의 정제방법과 동일하게 하는 경우, 상기 수득단계에서 수득되는 신너 조성물(잔류물)에는 신너용 화합물이 잔류물의 총중량 대비 95 내지 98중량%로 함유되게 되며, 상기 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되게 되며, 1-메톡시-2-프로판올아세테이트 50 내지 60중량부, 2-하이드록시이소부티릭엑시드메틸에스터 23 내지 30중량부 및 에틸락테이트 12 내지 16중량부를 포함하게 된다.The obtaining step is to recover the residue remaining in the reactor after the low boiling point material removal step to obtain a thinner composition, in the obtaining step to recover the liquid residue remaining in the reactor, or to recover the residue By distillation and recovery (distillate is recovered from when it reaches 135 ° C and recovered until it reaches 157 ° C), the thinner composition is obtained. In the thinner composition (residue) obtained in the obtaining step, the thinner compound is contained in an amount of 97 to 99% by weight relative to the total weight of the residue, and the thinner composition is used in a rinsing process for cleaning the photoresist during display manufacturing. 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 8 to 10 parts by weight of 2-hydroxyisobutyric acid methyl ester and 16 to 20 parts by weight of ethyl lactate. When the distillate in the recovery step is recovered from 132 ℃ to be recovered until 160 ℃, the low boiling point in the removal step of the low boiling point impurities from 73 ℃ when the removal starts from 142 ℃ Except to remove until, other conditions are the same as the purification method of the thinner waste liquid, the thinner composition (residue) obtained in the obtaining step contains 95 to 98% by weight of the compound for thinner relative to the total weight of the residue The thinner composition is used in the rinsing process for cleaning the photoresist during the display manufacturing process, 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester 23 to 30 parts by weight and 12 to 16 parts by weight of ethyl lactate.

본 발명의 다른 실시예에 따른 신너 폐액의 정제방법은 신너 폐액에서 공비혼합물이 형성되는 공비혼합물형성단계와, 신너 폐액을 반응기에 넣고 증류하여 신너용 화합물보다 저비점을 가지는 저비점불순물을 증류제거하는 저비점불순물제거단계와, 상기 저비점불순물제거단계 후 상기 반응기에 잔류하는 잔류물을 회수하는 잔류물회수단계와, 상기 잔류물을 반응기에서 증류하여 신너용 화합물보다 고비점을 가지는 고비점불순물이 제거된 증류물을 증류회수하여 신너 조성물을 수득하는 조성물수득단계와, 상기 조성물수득단계 후 상기 반응기에 잔류한 고비점불순물을 제거하는 고비점불순물제거단계를 포함한다. 본 발명의 다른 실시예에 따른 신너 폐액의 정제방법은, 고비점불순물을 먼저 제거하고 나중에 저비점불순물을 제거하여 신너 조성물을 수득하는 본 발명의 일 실시예에 따른 신너 폐액이 정제방법과 달리, 저비점불순물을 먼저 제거하고 나중에 고비점불순물을 제거하여 신너 조성물을 수득하는 차이만 있을 뿐이므로, 공통되는 부분에 대해서는 자세한 설명을 생략하기로 한다.According to another embodiment of the present invention, a method for purifying thinner waste liquid includes an azeotropic mixture forming step in which an azeotrope is formed in the thinner waste liquid, and a low boiling point for distilling low boiling point impurities having a lower boiling point than the compound for thinner by distilling the thinner waste liquid into a reactor. An impurity removal step, a residue recovery step of recovering the residue remaining in the reactor after the low boiling point impurity removal step, and distillation in which the high boiling point impurity having a higher boiling point than the thinner compound is removed by distilling the residue in the reactor. And a high boiling point impurity removal step of removing the high boiling point impurities remaining in the reactor after the composition obtaining step. The thinner waste liquid purifying method according to another embodiment of the present invention has a low boiling point unlike the purification method of the thinner waste liquid according to an embodiment of the present invention, in which a high boiling point impurities are first removed and later, the low boiling point impurities are removed to obtain a thinner composition. Since there is only a difference that the impurities are first removed and later the high boiling point impurities are removed to obtain the thinner composition, detailed descriptions of common parts will be omitted.

상기 저비점불순물제거단계는 신너 폐액을 반응기에 넣고 증류하여 신너용 화합물보다 저비점을 가지는 저비점불순물을 증류제거하는 단계이다. 상기 저비점물질제거단계에서 저비점불순물은 73℃가 될 때부터 제거가 시작되어 145℃가 될 때까지 제거되는 것이 바람직하다.The low boiling point impurities removal step is a step of distilling out the low boiling point impurities having a lower boiling point than the thinner waste liquid by distilling the reactor. In the low boiling point material removing step, the low boiling point impurity is preferably removed until it reaches 145 ° C from when the removal starts from 73 ° C.

상기 잔류물회수단계는 상기 저비점불순물제거단계 후 상기 반응기에 잔류하는 잔류물을 회수하는 단계이다.The residue recovery step is a step of recovering the residue remaining in the reactor after the low boiling point impurities removal step.

상기 조성물수득단계는 상기 잔류물을 반응기에서 증류하여 신너용 화합물보다 고비점을 가지는 고비점불순물이 제거된 증류물을 증류회수하여 신너 조성물을 수득하는 단계이다. 상기 조성물수득단계에서 증류물은 135℃가 될 때부터 회수가 시작되어 157℃가 될 때까지 회수되는 것이 바람직하다. 상기 조성물수득단계에서 수득되는 신너 조성물(증류물)에는 신너용 화합물이 증류물의 총중량 대비 97 내지 99중량%로 함유되게 되며, 상기 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되게 되며, 1-메톡시-2-프로판올아세테이트 65 내지 75중량부, 2-하이드록시이소부티릭엑시드메틸에스터 8 내지 10중량부 및 에틸락테이트 16 내지 20중량부를 포함하게 된다.The composition obtaining step is to obtain a thinner composition by distilling the residue from the reactor to distill the distillate from which the high boiling point impurities having a higher boiling point than the thinner compound are removed. In the composition obtaining step, the distillate is preferably recovered from when it reaches 135 ° C until it reaches 157 ° C. The thinner composition (distillate) obtained in the composition acquisition step will contain 97 to 99% by weight of the thinner compound relative to the total weight of the distillate, and the thinner composition may be used in a rinsing process for cleaning the photoresist during display manufacturing. 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 8 to 10 parts by weight of 2-hydroxyisobutyric acid methyl ester and 16 to 20 parts by weight of ethyl lactate.

상기 고비점불순물제거단계는 상기 조성물수득단계 후 상기 반응기에 잔류한 고비점불순물을 제거하는 단계로, 에틸-3-에톡시 프로피오네이트를 제거하는 이이피제거단계와, 에틸-3-에톡시 프로피오네이트를 제외한 고비점불순물을 제거하는 기타고비점불순물제거단계를 포함한다. 상기 저비점물질제거단계에서 저비점불순물이 73℃가 될 때부터 제거가 시작되어 142℃가 될 때까지 제거되고, 상기 조성물수득단계에서 증류물이 132℃가 될 때부터 회수가 시작되어 160℃가 될 때까지 회수되는 것을 제외하고, 다른 조건을 상기 본 발명의 다른 실시예에 따른 신너 폐액의 정제방법과 동일하게 하는 경우, 상기 조성물수득단계에서 수득되는 신너 조성물(증류물)에는 신너용 화합물이 증류물의 총중량 대비 95 내지 98중량%로 함유되게 되며, 상기 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되게 되며, 1-메톡시-2-프로판올아세테이트 50 내지 60중량부, 2-하이드록시이소부티릭엑시드메틸에스터 23 내지 30중량부 및 에틸락테이트 12 내지 16중량부를 포함하게 된다.The high boiling point impurity removing step is to remove the high boiling point impurities remaining in the reactor after the composition obtaining step, an IP removal step of removing ethyl-3-ethoxy propionate, and ethyl-3-ethoxy And other high boiling impurity removal steps to remove high boiling impurity except propionate. In the low boiling point material removing step, the low boiling point impurity is removed from 73 ° C. until it is removed until 142 ° C., and in the obtaining step of the composition, recovery is started at 160 ° C. when the distillate becomes 132 ° C. Except for recovery until the other conditions are the same as the method for purifying thinner waste liquid according to another embodiment of the present invention, the thinner composition (distillate) obtained in the composition obtaining step is a distillation compound for thinner 95 to 98% by weight relative to the total weight of water, the thinner composition is used in the rinsing process for cleaning the photoresist during the display manufacturing process, 50-60 parts by weight of 1-methoxy-2-propanol acetate, 2- It will comprise 23 to 30 parts by weight of hydroxyisobutyric acid methyl ester and 12 to 16 parts by weight of ethyl lactate.

본 발명의 또 다른 실시예는 앞서 설명한 신너 폐액의 정제방법에 의해 수득되는 신너 조성물에 대한 것이다. 상기 신너 조성물은 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하며, 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액으로 유래되고, 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되는 것을 특징으로 한다.Another embodiment of the present invention relates to a thinner composition obtained by the method for purifying thinner waste solution described above. The thinner composition includes 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate, and is used as waste liquid of thinner used in a rinsing process for cleaning photoresist during semiconductor manufacturing. It is derived from, characterized in that used in the rinse process for cleaning the photoresist during the display manufacturing process.

본 발명의 또 다른 실시예에 따른 신너 조성물은 1-메톡시-2-프로판올아세테이트 65 내지 75중량부, 2-하이드록시이소부티릭엑시드메틸에스터 8 내지 10중량부 및 에틸락테이트 16 내지 20중량부를 포함한다.The thinner composition according to another embodiment of the present invention is 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 8 to 10 parts by weight of 2-hydroxyisobutyric acid methyl ester and 16 to 20 parts by weight of ethyl lactate. Contains wealth.

본 발명의 또 다른 실시예에 다른 신너 조성물은 1-메톡시-2-프로판올아세테이트 50 내지 60중량부, 2-하이드록시이소부티릭엑시드메틸에스터 23 내지 30중량부 및 에틸락테이트 12 내지 16중량부를 포함한다.Another thinner composition according to another embodiment of the present invention is 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 23 to 30 parts by weight of 2-hydroxyisobutyric acid methyl ester and 12 to 16 parts by weight of ethyl lactate. Contains wealth.

이하, 실시예를 통해서 본 발명을 보다 상세히 설명하기로 한다 하지만, 이들은 본 발명을 보다 상세하게 설명하기 위한 것일 뿐, 본 발명의 권리범위가 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but these are merely for explaining the present invention in more detail, and the scope of the present invention is not limited thereto.

<실시예 1><Example 1>

(1) 반도체 제조공정 중 포토레지스트를 세정하는 린스공정에서 나온 1-메톡시-2-프로판올아세테이트 27중량%, 2-하이드록시이소부티릭엑시드메틸에스터 13중량%, 에틸락테이트 10중량%, 에틸-3-에톡시 프로피오네이트 36중량%, 물 1중량% 및 기타 불순물(1-메톡시-2-프로판올, N-부틸 아세테이트, 사이클로헥사논, 감마부티로락톤 및 이소프로판올을 포함하고 각각 동일한 양으로 이루어짐) 13중량%로 이루어진 신너 폐액(1kg)을 증류기를 이용하여 증류하여, 온도가 140℃가 될 때부터 증류물의 회수를 시작하여 152℃가 될 때까지 증류물을 회수하였다.(1) 27% by weight of 1-methoxy-2-propanol acetate from the rinse step of washing the photoresist during the semiconductor manufacturing process, 13% by weight of 2-hydroxyisobutyric acid methyl ester, 10% by weight of ethyl lactate, 36 wt% ethyl-3-ethoxy propionate, 1 wt% water and other impurities (1-methoxy-2-propanol, N-butyl acetate, cyclohexanone, gammabutyrolactone and isopropanol, each identical Thinner waste (1 kg) consisting of 13% by weight was distilled using a distiller to recover the distillate from when the temperature reaches 140 ° C until the temperature reaches 152 ° C.

(2) 회수된 증류물(액체상태)을 증류기를 이용하여 다시 증류하여, 새로운 증류물(저비점불순물)을 형성하고 온도가 78℃가 될 때부터 증류물의 제거를 시작하여 140℃가 될 때까지 증류물을 제거하였다. 이후, 증류기에 잔류하는 잔류물을 회수하여 측정 결과, 1-메톡시-2-프로판올아세테이트 70.5중량%, 2-하이드록시이소부티릭엑시드메틸에스터 9.1중량%, 에틸락테이트 18중량%, 에틸-3-에톡시 프로피오네이트 0.16중량%, 물 0.01중량% 및 기타 불순물 2.39중량%로 이루어진 신너 조성물 300g을 얻을 수 있었다.(2) The recovered distillate (liquid state) is distilled again using a distillation machine to form a new distillate (low boiling point impurity) and the removal of the distillate starts until the temperature reaches 78 ° C until the temperature reaches 140 ° C. Distillate was removed. Thereafter, the residue remaining in the distillation was recovered. As a result of measurement, 70.5% by weight of 1-methoxy-2-propanol acetate, 9.1% by weight of 2-hydroxyisobutyric acid methyl ester, 18% by weight of ethyl lactate, and ethyl- 300 g of thinner composition consisting of 0.16% by weight of 3-ethoxy propionate, 0.01% by weight of water and 2.39% by weight of other impurities could be obtained.

<실시예 2> <Example 2>

실시예 1의 (1)에서 온도가 137℃가 될 때부터 증류물의 회수를 시작하여 155℃가 될 때까지 증류물을 회수하고, 실시예 1의 (2)에서 온도가 78℃가 될 때부터 증류물의 제거를 시작하여 137℃가 될 때까지 증류물을 제거한 것을 제외하고는 다른 조건을 실시예 1과 동일하게 하여 잔류물을 회수하였다. 이후, 증류기에 잔류하는 잔류물을 회수하여 측정 결과, 1-메톡시-2-프로판올아세테이트 54.5중량%, 2-하이드록시이소부티릭엑시드메틸에스터 26.5중량%, 에틸락테이트 14중량%, 에틸-3-에톡시 프로피오네이트 0중량%, 물 0.01중량% 및 기타 불순물 4.99중량%로 이루어진 신너 조성물 520g을 얻을 수 있었다.From the time when the temperature became 137 degreeC in Example 1 (1), collection | recovery of distillate is started and the distillate is collect | recovered until it becomes 155 degreeC, and when the temperature becomes 78 degreeC in Example 1 (2), The residue was recovered in the same manner as in Example 1 except that the distillate was removed until the distillate was started and reached to 137 ° C. Thereafter, the residue remaining in the distillation was recovered. As a result of measurement, 54.5% by weight of 1-methoxy-2-propanol acetate, 26.5% by weight of 2-hydroxyisobutyric acid methyl ester, 14% by weight of ethyl lactate, and ethyl- 520 g of thinner composition consisting of 0% by weight of 3-ethoxy propionate, 0.01% by weight of water and 4.99% by weight of other impurities could be obtained.

<비교예>Comparative Example

(1) 비교예 1(1) Comparative Example 1

1-메톡시-2-프로판올아세테이트 70중량부 및 1-메톡시-2-프로판올 30중량부로 이루어진 신너 조성물을 형성하였다.A thinner composition consisting of 70 parts by weight of 1-methoxy-2-propanol acetate and 30 parts by weight of 1-methoxy-2-propanol was formed.

(2) 비교예 2(2) Comparative Example 2

실시예 1에서 얻은 신너 조성물에 에틸-3-에톡시 프로피오네이트를 추가로 첨가하여, 1-메톡시-2-프로판올아세테이트 70.5중량부, 2-하이드록시이소부티릭엑시드메틸에스터 9.1중량부, 에틸락테이트 18중량부, 에틸-3-에톡시 프로피오네이트 2.16중량부, 물 0.01중량부 및 기타 불순물 2.39중량부로 이루어진 신너 조성물을 형성하였다.Ethyl-3-ethoxy propionate was further added to the thinner composition obtained in Example 1, 70.5 parts by weight of 1-methoxy-2-propanol acetate, 9.1 parts by weight of 2-hydroxyisobutyric acid methyl ester, A thinner composition was formed consisting of 18 parts by weight of ethyl lactate, 2.16 parts by weight of ethyl-3-ethoxy propionate, 0.01 part by weight of water, and 2.39 parts by weight of other impurities.

(3) 비교예 3(3) Comparative Example 3

실시예 1에서 얻은 신너 조성물에 물 추가로 첨가하여, 1-메톡시-2-프로판올아세테이트 70.5중량부, 2-하이드록시이소부티릭엑시드메틸에스터 9.1중량부, 에틸락테이트 18중량부, 에틸-3-에톡시 프로피오네이트 0.16중량부, 물 1.01중량부 및 기타 불순물 2.39중량로 이루어진 신너 조성물을 형성하였다.To the thinner composition obtained in Example 1, water was further added, and 70.5 parts by weight of 1-methoxy-2-propanol acetate, 9.1 parts by weight of 2-hydroxyisobutyric acid methyl ester, 18 parts by weight of ethyl lactate, and ethyl- A thinner composition consisting of 0.16 parts by weight of 3-ethoxy propionate, 1.01 part by weight of water and 2.39 parts by weight of other impurities was formed.

(4) 비교예 4(4) Comparative Example 4

1-메톡시-2-프로판올아세테이트 54.5중량부, 2-하이드록시이소부티릭엑시드메틸에스터 26.5중량부, 에틸락테이트 14중량부, 에틸-3-에톡시 프로피오네이트 0중량부 및 물 0.01중량부로 이루어진 신너 조성물을 형성하였다.54.5 parts by weight of 1-methoxy-2-propanol acetate, 26.5 parts by weight of 2-hydroxyisobutyric acid methyl ester, 14 parts by weight of ethyl lactate, 0 parts by weight of ethyl-3-ethoxy propionate and 0.01 weight of water A thinner composition consisting of parts was formed.

(5) 비교예 5(5) Comparative Example 5

1-메톡시-2-프로판올아세테이트 40중량부, 2-하이드록시이소부티릭엑시드메틸에스터 30중량부, 에틸락테이트 30중량부로 이루어진 신너 조성물을 형성하였다.A thinner composition consisting of 40 parts by weight of 1-methoxy-2-propanol acetate, 30 parts by weight of 2-hydroxyisobutyric acid methyl ester, and 30 parts by weight of ethyl lactate was formed.

<실험예> 신너 조성물의 포토레지스트 세정력 실험<Experimental example> Experiment of photoresist cleaning power of thinner composition

(1) 슬라이드 글라스에 디스플레이 제조공정에서 사용하는 상용화된 포토레지스트를 도포하고 80℃ 오븐에서 1시간 동안 soft baking을 실시하여, 도 1에 도시된 바와 같은 시편을 준비하였다. 100ml 비이커에 실시예 1, 2 및 비교예 1 내지 5의 신너 조성물(50ml) 각각을 넣은 후, 상기 비이커를 초음파 세척기에 넣고 상기 비이커에 상기 시편을 완전히 침지시킨 후 초음파 세척기를 작동시켰다.(1) A commercially available photoresist used in a display manufacturing process was applied to a slide glass, and soft baking was performed for 1 hour in an oven at 80 ° C. to prepare a specimen as shown in FIG. 1. After each of the thinner compositions (50 ml) of Examples 1 and 2 and Comparative Examples 1 to 5 were placed in a 100 ml beaker, the beaker was placed in an ultrasonic cleaner, and the sample was completely immersed in the beaker, and then the ultrasonic cleaner was operated.

(2) 실시예 및 비교예에 따른 신너 조성물이 대표적인 상용화된 디스플레이용 신너인 비교예 1보다 포토레지스트 세정력이 뛰어나는지 확인하기 위해, 실험예 (1)에서 초음파 세척기를 작동시킨 후 10초가 지난 시점에서 각 시편을 육안으로 확인하여, 비교예 1의 신너 조성물이 사용된 경우보다 포토레지스트 세정력이 좋은지 나쁜지 판단하여 표 1에 나타내었다. 표 1을 보면, 실시예 1, 2 및 비교예 4의 경우 비교예 1보다 포토레지스트 세정력이 뛰어남을 알 수 있어 본 발명에 따라 따라 수득된 신너 조성물이 디스플레이용 신너로 사용될 수 있음을 알 수 있고, 비교예 2, 3 및 5는 비교에 1보다 포토레지스트 세정력이 낮음을 알 수 있는데 이를 통해, 에틸-3-에톡시 프로피오네이트, 수분은 세정력을 떨어뜨리며, 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트로 이루어져도 특정 비율로 혼합되지 않으면 디스플레이용 신너의 역할을 수행하지 못함을 알 수 있다.(2) In order to confirm whether the thinner composition according to the Examples and Comparative Examples is superior in photoresist cleaning power than Comparative Example 1, which is a typical commercially available display thinner, 10 seconds after operating the ultrasonic cleaner in Experimental Example (1) Each specimen was visually checked at to determine whether the photoresist cleaning power was better or worse than that in the thinner composition of Comparative Example 1, and is shown in Table 1 below. Looking at Table 1, it can be seen that in Example 1, 2 and Comparative Example 4, the photoresist cleaning power is superior to Comparative Example 1, so that the thinner composition obtained according to the present invention can be used as a display thinner. , Comparative Examples 2, 3 and 5 can be seen that the photoresist cleaning power is lower than 1 in comparison, through this, ethyl-3-ethoxy propionate, water is deteriorating the cleaning power, 1-methoxy-2-propanol Even if it consists of acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate, it can be seen that it does not serve as a display thinner unless mixed in a specific ratio.

실시예 1Example 1 실시예 2Example 2 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 1대비 세정력Cleaning power compared to Comparative Example 1 좋음good 좋음good 나쁨Bad 나쁨Bad 좋음good 나쁨Bad

(3) 본 발명의 실시예들과 대표적인 상용화된 디스플레이용 신너인 비교예 1의 포토레지스트 세정력을 정밀 비교하기 위해, 실험예 (1)에서 초음파 세척기를 작동시킨 후, 1, 3, 5 및 10초가 지난 시점에서 실시예 1, 2 및 비교예 1이 각각 사용된 시편을 꺼내 촬영하여 도 2에 나타내었고, 또한 포토레지스트가 슬라이드 글라스에서 완전히 제거된 시간을 측정하여 표 2에 나타내었다. 도 2 및 표 2를 보면, 실시예 1 및 2가 비교예 1에 비해 현저하게 세정력이 더 뛰어남을 알 수 있고, 실시예 1이 실시예 2보다 세정력이 뛰어남을 알 수 있다.(3) In order to precisely compare the photoresist cleaning power of Comparative Example 1, which is a typical commercial display thinner with the embodiments of the present invention, after operating the ultrasonic cleaner in Experimental Example (1), 1, 3, 5, and 10 At the end of the second, the specimens in which Examples 1, 2 and Comparative Example 1 were used were taken out and photographed, respectively, and are shown in FIG. 2, and the times when the photoresist was completely removed from the slide glass were measured. 2 and Table 2, it can be seen that Examples 1 and 2 are significantly more excellent cleaning power than Comparative Example 1, Example 1 is superior to Example 2 cleaning power.

실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 제거 시간(s)Removal time (s) 16.416.4 20.420.4 38.1538.15

(4) 기타 불순물의 유무에 따른 세정력을 비교하기 위해, 실험예 (1)에서 초음파 세척기를 작동시킨 후, 실시예 2 및 비교예 4가 각각 사용된 시편을 육안으로 확인하여 포토레지스트가 슬라이드 글라스에서 완전히 제거된 시간을 측정한 결과, 실시예 2의 경우 20.4초가 지난후 포토레지스트가 완전히 제거되었고 비교예 4의 경우 19.8초가 지난 후 포토레지스트가 완전히 제거되었다. 이를 통해 신너 조성물에 기타 불순물이 소량(대략 6중량% 미만)으로 혼합되어 있어도 포토레지스트 세정력에는 영향을 끼지 않음을 알 수 있다.(4) In order to compare the cleaning power according to the presence or absence of other impurities, after operating the ultrasonic cleaner in Experimental Example (1), the specimens used in Example 2 and Comparative Example 4 were visually confirmed, and the photoresist was slide glass. As a result, the photoresist was completely removed after 20.4 seconds in Example 2 and completely removed after 19.8 seconds in Comparative Example 4. It can be seen that even if a small amount (about 6% by weight or less) of other impurities is mixed in the thinner composition, the photoresist cleaning power is not affected.

(5) 위의 실험 결과를 통해, 본 발명의 정제방법에 의해 제조된 실시예 1 및 2의 신너 조성물은 대표적인 상용화된 디스플레이용 신너(비교예 1)보다 세정력이 뛰어남을 알 수 있고, 실시예 2에 따른 정제방법이 회수율을 현저하게 증가시킬 수 있음을 알 수 있다.(5) Through the above experimental results, it can be seen that the thinner compositions of Examples 1 and 2 prepared by the purification method of the present invention are superior in cleaning power than typical commercially available display thinners (Comparative Example 1). It can be seen that the purification method according to 2 can significantly increase the recovery rate.

이상에서, 출원인은 본 발명의 다양한 실시예들을 설명하였지만, 이와 같은 실시예들은 본 발명의 기술적 사상을 구현하는 일 실시예일 뿐이며, 본 발명의 기술적 사상을 구현하는 한 어떠한 변경예 또는 수정예도 본 발명의 범위에 속하는 것으로 해석되어야 한다.In the above, the Applicant has described various embodiments of the present invention, but these embodiments are merely one embodiment for implementing the technical idea of the present invention, and any changes or modifications may be made to the present invention as long as the technical idea of the present invention is implemented. It should be interpreted as falling within the scope of.

Claims (27)

신너 폐액을 반응기에 넣고 증류하여 신너용 화합물보다 고비점을 가지는 고비점불순물이 제거된 증류물을 증류회수하는 회수단계와;A distillation step of distilling the thinner waste solution into the reactor and distilling the distillate from which the high boiling point impurities having a higher boiling point than the thinner compound are removed; 상기 회수단계 후 상기 반응기에 잔류한 고비점불순물을 제거하는 고비점물질제거단계와;A high boiling point material removing step of removing the high boiling point impurities remaining in the reactor after the recovering step; 상기 증류물을 반응기에 넣고 증류하여 신너용 화합물보다 저비점을 가지는 저비점불순물을 증류제거하는 저비점물질제거단계와;A low boiling point material removing step of distilling the distillate into a reactor and distilling a low boiling point impurity having a lower boiling point than a compound for thinner; 상기 저비점물질제거단계 후 상기 반응기에 잔류하는 잔류물을 회수하여 신너 조성물을 수득하는 수득단계;를 포함하는 것을 특징으로 하는 신너 폐액의 정제방법.And a step of obtaining the thinner composition by recovering the residue remaining in the reactor after the low boiling point material removing step. 제1항에 있어서,The method of claim 1, 상기 신너 폐액의 정제방법은 신너 폐액에서 공비혼합물이 형성되는 공비혼합물형성단계를 추가로 포함하며,The method for purifying thinner waste further includes an azeotrope forming step in which an azeotrope is formed in the thinner waste, 상기 회수단계에서 상기 신너 폐액은 공비혼합물이 형성된 신너 폐액이 사용되고,In the recovery step, the thinner waste liquid is a thinner waste liquid in which an azeotrope is formed, 상기 고비점불순물은 상기 신너용 화합물보다 고비점을 가지는 화합물 및 상기 신너용 화합물보다 고비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하며,The high boiling point impurity includes any one or more of a compound having a higher boiling point than the compound for thinner and an azeotrope having a higher boiling point than the compound for thinner, 상기 저비점불순물은 상기 신너용 화합물보다 저비점을 가지는 화합물 및 상기 신너용 화합물보다 저비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하는 것을 특징을 하는 신너 폐액의 정제방법.The low boiling point impurity comprises at least one of a compound having a lower boiling point than the compound for thinner and an azeotrope having a lower boiling point than the compound for thinner. 제1항에 있어서, 상기 신너 폐액은The method of claim 1, wherein the thinner waste liquid 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터, 에틸락테이트 및 불순물을 포함하는 것을 특징으로 하는 신너 폐액의 정제방법.A method for purifying thinner waste, comprising 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester, ethyl lactate, and impurities. 제1항에 있어서, 상기 고비점물질제거단계는According to claim 1, The high boiling point material removing step 에틸-3-에톡시 프로피오네이트를 제거하는 이이피제거단계를 포함하는 것을 특징으로 하는 신너 폐액을 정제방법.A method for purifying thinner waste, comprising an elimination step of removing ethyl-3-ethoxy propionate. 제1항에 있어서, 상기 신너 폐액은The method of claim 1, wherein the thinner waste liquid 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액이 이용되는 것을 특징으로 하는 신너 폐액의 정제방법.A method for purifying thinner waste, characterized in that the waste liquid of the thinner used in the rinsing step of cleaning the photoresist is used. 제1항에 있어서,The method of claim 1, 상기 수득단계에서 수득되는 상기 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되는 것을 특징으로 하는 신너 폐액의 정제방법.The thinner composition obtained in the obtaining step is used in a rinsing process for cleaning a photoresist during a display manufacturing process. 제1항에 있어서, 상기 신너용 화합물은The compound for thinner according to claim 1, wherein 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하는 것을 특징으로 하는 신너 폐액의 정제방법.A method for purifying thinner waste, comprising 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate. 제1항에 있어서, 상기 수득단계에서는The method of claim 1, wherein in the obtaining step 반응기에 잔류하는 액체 상태의 잔류물을 회수하거나, 상기 잔류물을 다시 증류하여 회수하여, 상기 신너 조성물을 얻는 것을 특징으로 하는 신너 폐액의 정제방법.A liquid residue remaining in a reactor is recovered, or the residue is distilled off and recovered to obtain the thinner composition. 제1항에 있어서,The method of claim 1, 상기 회수단계에서 증류물은 135℃가 될 때부터 회수가 시작되어 157℃가 될 때까지 회수되며,In the recovery step, the distillate is recovered from when it reaches 135 ° C. and recovered until it reaches 157 ° C., 상기 저비점물질제거단계에서 저비점불순물은 73℃가 될 때부터 제거가 시작되어 145℃가 될 때까지 제거되는 것을 특징으로 하는 신너 폐액의 정제방법.In the low boiling point material removal step, the low boiling point impurities are removed from 73 ° C. until the removal starts until 145 ° C. 제1항에 있어서,The method of claim 1, 상기 회수단계에서 증류물은 132℃가 될 때부터 회수가 시작되어 160℃가 될 때까지 회수되며,In the recovery step, the distillate is recovered from when it reaches 132 ° C and is recovered until it reaches 160 ° C, 상기 저비점물질제거단계에서 저비점불순물은 73℃가 될 때부터 제거가 시작되어 142℃가 될 때까지 제거되는 것을 특징으로 하는 신너 폐액의 정제방법.In the low boiling point material removing step, the low boiling point impurities are removed starting from 73 ° C. until the 142 ° C. purification method for thinner waste liquid. 제1항 내지 제10항 중 어느 한 항의 정제방법으로부터 수득되는 것을 특징으로 하는 신너 조성물.The thinner composition obtained from the purification method of any one of Claims 1-10. 제11항에 있어서, 상기 신너 조성물은The method of claim 11, wherein the thinner composition 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하는 것을 특징으로 하는 신너 조성물.A thinner composition comprising 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate. 제11항에 있어서, 상기 신너 조성물은The method of claim 11, wherein the thinner composition 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되는 것을 특징으로 하는 신너 조성물.Thinner composition, characterized in that used in the rinse process for cleaning the photoresist during the display manufacturing process. 제9항의 정제방법으로부터 수득되며,Obtained from the purification method of claim 9, 1-메톡시-2-프로판올아세테이트 65 내지 75중량부, 2-하이드록시이소부티릭엑시드메틸에스터 8 내지 10중량부 및 에틸락테이트 16 내지 20중량부를 포함하는 것을 특징으로 하는 신너 조성물.A thinner composition comprising 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 8 to 10 parts by weight of 2-hydroxyisobutyric acid methyl ester, and 16 to 20 parts by weight of ethyl lactate. 제10항의 정제방법으로부터 수득되며,Obtained from the purification method of claim 10, 1-메톡시-2-프로판올아세테이트 50 내지 60중량부, 2-하이드록시이소부티릭엑시드메틸에스터 23 내지 30중량부 및 에틸락테이트 12 내지 16중량부를 포함하는 것을 특징으로 하는 신너 조성물.A thinner composition comprising 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 23 to 30 parts by weight of 2-hydroxyisobutyric acid methyl ester, and 12 to 16 parts by weight of ethyl lactate. 신너 폐액을 반응기에 넣고 증류하여 신너용 화합물보다 저비점을 가지는 저비점불순물을 증류제거하는 저비점불순물제거단계와;A low boiling point impurity removal step of distilling the thinner waste solution into the reactor to distill off the low boiling point impurity having a lower boiling point than the thinner compound; 상기 저비점불순물제거단계 후 상기 반응기에 잔류하는 잔류물을 회수하는 잔류물회수단계와;A residue recovery step of recovering the residue remaining in the reactor after the low boiling point impurities removal step; 상기 잔류물을 반응기에서 증류하여 신너용 화합물보다 고비점을 가지는 고비점불순물이 제거된 증류물을 증류회수하여 신너 조성물을 수득하는 조성물수득단계와;Distilling the residue from the reactor to obtain a thinner composition by distilling a distillate from which a high boiling point impurity having a higher boiling point is removed than a compound for thinner; 상기 조성물수득단계 후 상기 반응기에 잔류한 고비점불순물을 제거하는 고비점불순물제거단계를 포함하는 것을 특징으로 하는 신너 폐액의 정제방법.And a high boiling point impurity removal step of removing the high boiling point impurity remaining in the reactor after the composition obtaining step. 제16항에 있어서,The method of claim 16, 상기 신너 폐액의 정제방법은 신너 폐액에서 공비혼합물이 형성되는 공비혼합물형성단계를 추가로 포함하며,The method for purifying thinner waste further includes an azeotrope forming step in which an azeotrope is formed in the thinner waste, 상기 저비점불순물제거단계에서 상기 신너 폐액은 공비혼합물이 형성된 신너 폐액이 사용되고,In the low boiling point impurities removal step, the thinner waste liquid is used as a thinner waste liquid in which an azeotrope is formed. 상기 저비점불순물은 상기 신너용 화합물보다 저비점을 가지는 화합물 및 상기 신너용 화합물보다 저비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하며,The low boiling point impurities include any one or more of a compound having a lower boiling point than the compound for thinners and an azeotrope having a lower boiling point than the compound for thinners, 상기 고비점불순물은 상기 신너용 화합물보다 고비점을 가지는 화합물 및 상기 신너용 화합물보다 고비점을 가지는 공비혼합물 중 어느 하나 이상을 포함하는 것을 특징을 하는 신너 폐액의 정제방법.The high boiling point impurity comprises at least one of a compound having a higher boiling point than the compound for thinner and an azeotrope having a higher boiling point than the compound for thinner. 제16항에 있어서, 상기 신너 폐액은The method of claim 16, wherein the thinner waste liquid 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터, 에틸락테이트 및 불순물을 포함하는 것을 특징으로 하는 신너 폐액의 정제방법.A method for purifying thinner waste, comprising 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester, ethyl lactate, and impurities. 제16항에 있어서, 상기 고비점불순물제거단계는The method of claim 16, wherein the high boiling point impurities removal step 에틸-3-에톡시 프로피오네이트를 제거하는 이이피제거단계를 포함하는 것을 특징으로 하는 신너 폐액을 정제방법.A method for purifying thinner waste, comprising an elimination step of removing ethyl-3-ethoxy propionate. 제16항에 있어서, 상기 신너 폐액은The method of claim 16, wherein the thinner waste liquid 반도체 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용된 신너의 폐액이 이용되는 것을 특징으로 하는 신너 폐액의 정제방법.A method for purifying thinner waste, characterized in that the waste liquid of the thinner used in the rinsing step of cleaning the photoresist is used. 제16항에 있어서, The method of claim 16, 상기 조성물수득단계에서 수득되는 상기 신너 조성물은 디스플레이 제조과정 중 포토레지스터를 세정하는 린스공정에서 사용되는 것을 특징으로 하는 신너 폐액의 정제방법.The thinner composition obtained in the composition obtaining step is used in a rinsing process for cleaning a photoresist during a display manufacturing process. 제16항에 있어서, 상기 신너용 화합물은The compound of claim 16, wherein 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하는 것을 특징으로 하는 신너 폐액의 정제방법.A method for purifying thinner waste, comprising 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate. 제16항 내지 제22항 중 어느 한 항의 정제방법으로부터 수득되는 것을 특징으로 하는 신너 조성물.The thinner composition obtained from the purification method of any one of Claims 16-22. 제23항에 있어서, 상기 신너 조성물은The method of claim 23, wherein the thinner composition 1-메톡시-2-프로판올아세테이트, 2-하이드록시이소부티릭엑시드메틸에스터 및 에틸락테이트를 포함하는 것을 특징으로 하는 신너 조성물.A thinner composition comprising 1-methoxy-2-propanol acetate, 2-hydroxyisobutyric acid methyl ester and ethyl lactate. 제23항에 있어서, 상기 신너 조성물은The method of claim 23, wherein the thinner composition 디스플레이 제조과정 중 포토레지스트를 세정하는 린스공정에서 사용되는 것을 특징으로 하는 신너 조성물.Thinner composition, characterized in that used in the rinse process for cleaning the photoresist during the display manufacturing process. 제23항에 있어서, 상기 신너 조성물은The method of claim 23, wherein the thinner composition 1-메톡시-2-프로판올아세테이트 65 내지 75중량부, 2-하이드록시이소부티릭엑시드메틸에스터 8 내지 10중량부 및 에틸락테이트 16 내지 20중량부를 포함하는 것을 특징으로 하는 신너 조성물.A thinner composition comprising 65 to 75 parts by weight of 1-methoxy-2-propanol acetate, 8 to 10 parts by weight of 2-hydroxyisobutyric acid methyl ester, and 16 to 20 parts by weight of ethyl lactate. 제23항에 있어서, 상기 신너 조성물은The method of claim 23, wherein the thinner composition 1-메톡시-2-프로판올아세테이트 50 내지 60중량부, 2-하이드록시이소부티릭엑시드메틸에스터 23 내지 30중량부 및 에틸락테이트 12 내지 16중량부를 포함하는 것을 특징으로 하는 신너 조성물.A thinner composition comprising 50 to 60 parts by weight of 1-methoxy-2-propanol acetate, 23 to 30 parts by weight of 2-hydroxyisobutyric acid methyl ester, and 12 to 16 parts by weight of ethyl lactate.
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KR101384810B1 (en) * 2013-08-14 2014-04-15 덕산실업(주) Thinner for rinsing photoresist and the method of purifying the thinner
KR101446541B1 (en) * 2014-02-27 2014-10-06 주식회사 코렉스 Method for increasing recycle yield rate of waste high boiling point photoresist stripper
KR20150115457A (en) * 2014-04-04 2015-10-14 주식회사 엘지화학 Recovery method of stripper composition for photoresist
KR20160012721A (en) * 2014-07-25 2016-02-03 덕산실업(주) Purification method of thinner for rinsing photoresist
KR101939811B1 (en) * 2018-07-18 2019-01-18 덕산실업(주) Purification method of thinner waste and Thinner composition manufactured therefrom

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