Propylene glycol monomethyl ether acetate composition

Abstract

A propylene glycol monomethyl ether acetate composition containing propylene glycol 1-monomethyl ether 2-acetate, acetic acid, propionic acid, and water, wherein the content of the propionic acid is 2 ppm or more and 30 ppm or less with respect to 100 mass% of the propylene glycol monomethyl ether acetate composition, the sum of the contents of the acetic acid and the propionic acid is 5 ppm or more and 80 ppm or less with respect to 100 mass% of the propylene glycol monomethyl ether acetate composition, and the content of the water is 17 ppm or more and 250 ppm or less with respect to 100 mass% of the propylene glycol monomethyl ether acetate composition.

Description

TECHNICAL FIELD

[0001] The present application relates to a propylene glycol monomethyl ether acetate composition. BACKGROUND

[0002] Propylene glycol monomethyl ether acetate (hereinafter also referred to as "PMA") is known as an organic solvent used in various applications. PMA is produced, for example, by performing a direct esterification reaction of propylene glycol monomethyl ether (hereinafter also referred to as "PM") with acetic acid under prescribed conditions or the like (for example, refer to Patent Document 1).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: Chinese Patent Application Publication No. 1515537 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] The PMA obtained by the method described in Patent Document 1 was stored for a long period of time and the composition thereof was confirmed, as a result of which it was found that there was a tendency for the purity of the PMA to decrease.

[0008] The present application was completed in view of the above-described circumstances, and aims to provide a propylene glycol monomethyl ether acetate composition having excellent storage stability.

[0009] METHOD FOR SOLVING THE PROBLEM

[0010] The present inventors found that a propylene glycol monomethyl ether acetate composition containing prescribed components was able to solve the above-described problems, and thus completed the present application.

[0011] That is, the present application includes the following modes.

[0012] [1] A propylene glycol monomethyl ether acetate composition, which is a propylene glycol monomethyl ether acetate composition containing propylene glycol 1-monomethyl ether 2-acetate, acetic acid, propionic acid, and water, wherein,

[0013] the content of the propionic acid is 2 ppm or more and 30 ppm or less with respect to 100 mass% of the propylene glycol monomethyl ether acetate composition,

[0014] the sum of the contents of the acetic acid and the propionic acid is 5 ppm or more and 80 ppm or less with respect to 100 mass% of the propylene glycol monomethyl ether acetate composition,

[0015] the content of the water is 17 ppm or more and 250 ppm or less with respect to 100 mass% of the propylene glycol monomethyl ether acetate composition.

[0016] [2] The propylene glycol monomethyl ether acetate composition according to [1], wherein the content of propylene glycol monomethyl ether is 4.0 ppm or less with respect to 100 mass% of the propylene glycol monomethyl ether acetate composition.

[0017] [3] The propylene glycol monomethyl ether acetate composition according to [1] or [2], wherein the content of water is 20 ppm or more and 100 ppm or less with respect to 100 mass% of the propylene glycol monomethyl ether acetate composition.

[0018] [4] The propylene glycol monomethyl ether acetate composition according to any one of [1] to [3], wherein, in the case where the propylene glycol monomethyl ether acetate composition is subjected to the following test and then subjected to gas chromatography analysis under the following conditions, the area ratio of peaks appearing in the range of a relative retention time of 0.64 to 0.72 is 800 ppm or less when the relative retention time of a peak of propylene glycol 1-monomethyl ether 2-acetate is set to 1.00.

[0019] (Test)

[0020] The propylene glycol monomethyl ether acetate composition was heated to 80°C under a nitrogen atmosphere in a borosilicate glass container and left for 5 days.

[0021] (Conditions for gas chromatography analysis)

[0022] Analysis column: column having a fixed phase of polyethylene glycol, length 30 m x inner diameter 0.25 mm x film thickness 0.25 μm

[0023] Temperature rising conditions: 10 minutes at 50°C, then temperature rising at 5°C / minute to 250°C

[0024] Sample introduction temperature: 250°C

[0025] Carrier gas: nitrogen

[0026] Column gas flow rate: 1.0 mL / minute

[0027] Detector and detection temperature: hydrogen flame ionization detector, 250°C

[0028] Control mode: column flow rate

[0029] Split ratio: 50:1

[0030] Injection amount: 2.0 μL

[0031] Effects of the Invention

[0032] According to the present application, it is possible to provide a propylene glycol monomethyl ether acetate composition which is excellent in storage stability. DETAILED DESCRIPTION

[0033] Hereinafter, a mode for carrying out the present application (hereinafter referred to as "the present embodiment") will be explained in detail. The present embodiment is an example for explaining the present application, and is not intended to limit the present application to the following. The present application can be carried out with appropriate changes within the scope of the gist thereof.

[0034] <Propylene glycol monomethyl ether acetate composition>

[0035] The propylene glycol monomethyl ether acetate composition of the present embodiment (hereinafter also referred to as "PMA composition") is a propylene glycol monomethyl ether acetate composition containing propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as "PGMEA"), acetic acid, propionic acid and water, the content of the above-described propionic acid is 2 ppm or more and 30 ppm or less with respect to 100 mass% of the above-described propylene glycol monomethyl ether acetate composition, the sum of the contents of the above-described acetic acid and the above-described propionic acid is 5 ppm or more and 80 ppm or less with respect to 100 mass% of the above-described propylene glycol monomethyl ether acetate composition, and the content of the above-described water is 17 ppm or more and 250 ppm or less with respect to 100 mass% of the above-described propylene glycol monomethyl ether acetate composition. The PMA composition of the present embodiment is excellent in storage stability because of having such a constitution.

[0036] The reason why the PMA composition of the present embodiment is excellent in storage stability is presumed as follows, but is not necessarily clear, and is not intended to limit the reason thereof.

[0037] It is considered that one of the factors that affect the storage stability is that PGMEA is decomposed to generate impurities in the long-term storage of the propylene glycol monomethyl ether acetate composition. As a reason for the decomposition of the carboxylic acid ester such as PGMEA, for example, hydrolysis can be listed. Generally, in the presence of an acid and water, a carboxylic acid ester is hydrolyzed to become a carboxylic acid and an alcohol. Furthermore, it is considered that there is a tendency that the carboxylic acid ester is more easily hydrolyzed in the case where the content of the acid is large. However, it is considered that by making the content of the propionic acid, the sum of the content of the acetic acid and the content of the propionic acid, and the content of the water in the PMA composition of the present embodiment be within the above-described ranges, the alcohol that can be generated due to the hydrolysis of PGMEA and the ester exchange of the acetyl group of PGMEA can be suppressed, which is different from the above-described tendency, and the hydrolysis of PGMEA is suppressed.

[0038] However, the above-described reason can be considered only as one factor of the excellent storage stability of the PMA composition of the present embodiment, and the mechanism of action of the present embodiment is not limited thereto.

[0039] There is no particular limitation on the use of the PMA composition of the present embodiment, and for example, it can be used for industrial uses such as inks, diluents, pharmaceuticals / agrochemicals, plasticizers, surfactants, high molecular materials, lubricating oils, adhesives, cleaning agents, electronic materials, paints, and the like.

[0040] As an electronic material, there are no particular limitations; examples include liquid crystal displays (LCDs) and semiconductor devices. The PMA composition of this embodiment is preferably used in the manufacture of semiconductor devices due to its excellent storage stability.

[0041] Specific examples of applications related to the manufacture of semiconductor devices are not particularly limited, but can include: cleaning solutions (e.g., processing solutions for cleaning substrate surfaces after resist stripping), pre-wetting solutions (e.g., processing solutions used before resist coating to reduce the consumption of resist solvent), resist solvents (e.g., processing solutions for dissolving photosensitive agents and resins), developing solutions (e.g., processing solutions for removing soluble resins after exposure to negative resist), stripping solutions (e.g., processing solutions for removing cured resist after etching), etc. From the viewpoint of preventing defects in semiconductor device manufacturing, the PMA composition of this embodiment is preferably used for: resist solvents, pre-wetting solutions, solvents used for edge rinsing (rinsing to remove resist from the outer periphery of the wafer) and back-side rinsing (rinsing to remove resist from the back side of the wafer) during resist coating, developing solutions used during negative resist development, rinsing solutions used during rinsing after negative resist development, cleaning solutions or rinsing solutions used to remove resist after etching, etc.

[0042] (Propylene glycol 1-monomethyl ether 2-acetate)

[0043] The propylene glycol 1-monomethyl ether 2-acetic acid ester in the PMA composition of this embodiment can be identified and quantified, for example, by gas chromatography (hereinafter also referred to as "GC") analysis.

[0044] (Gas Chromatography Analysis)

[0045] Analytical column: A column with polyethylene glycol as the stationary phase, 30 m in length × 0.25 mm in inner diameter × 0.25 μm in film thickness.

[0046] Heating conditions: Hold at 50℃ for 10 minutes, then increase to 250℃ at a rate of 5℃ / minute.

[0047] Sample introduction temperature: 250℃

[0048] Carrier gas: Nitrogen

[0049] Column gas flow rate: 1.0 mL / min

[0050] Detector and detection temperature: Flame ionization detector, 250℃

[0051] Control mode: Column flow

[0052] Flow split ratio: 50:1

[0053] Injection volume: 2.0 μL

[0054] The content of PGMEA in the PMA composition of this embodiment can be appropriately determined according to the intended use of the PMA composition of this embodiment, and is not particularly limited. From the viewpoint of applications requiring high purity, the content is preferably 99.94% or more, more preferably 99.95% or more, and even more preferably 99.96% or more, based on the peak area ratio relative to the total peak area of ​​the spectrum obtained from the GC analysis. In this embodiment, "total peak area" refers to the sum of the areas of all peaks appearing in the spectrum obtained from the GC analysis. In this embodiment, "all peaks" can be specifically defined as all peaks that appear when the relative retention time of the PGMEA peak is set to 1.00, and analysis is continued from a relative retention time of 0.14 to 2.95 before analysis is stopped.

[0055] (acetic acid)

[0056] The PMA composition of this embodiment contains acetic acid. From the viewpoint of storage stability, the content of acetic acid in the PMA composition of this embodiment is preferably 3 ppm or more and 78 ppm or less, more preferably 5 ppm or more and 72 ppm or less, and even more preferably 7 ppm or more and 69 ppm or less, relative to 100% by mass of the PMA composition of this embodiment.

[0057] The above-mentioned content can be determined based on the methods described in the examples described later.

[0058] Regarding the aforementioned content, it can be adjusted to the above range, for example, by appropriately adding acetic acid or the like after performing the adsorption treatment described later. Furthermore, the aforementioned content can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and dehydration treatment (e.g., treatment time, etc.).

[0059] (propionic acid)

[0060] The PMA composition of this embodiment contains propionic acid. From the viewpoint of storage stability, the content of propionic acid in the PMA composition of this embodiment is 2 ppm or more and 30 ppm or less, preferably 3 ppm or more and 25 ppm or less, and more preferably 3 ppm or more and 20 ppm or less, relative to 100% by mass of the PMA composition of this embodiment.

[0061] The above-mentioned content can be determined based on the methods described in the examples described later.

[0062] Regarding the aforementioned content, it can be adjusted to the above range, for example, by appropriately adding propionic acid or the like after performing the adsorption treatment described later. Furthermore, the aforementioned content can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and dehydration treatment (e.g., treatment time, etc.).

[0063] (The sum of the contents of acetic acid and propionic acid)

[0064] In this embodiment, from the viewpoint of preserving stability, the sum of the content of acetic acid and propionic acid in the PMA composition of this embodiment is 5 ppm or more and 80 ppm or less, preferably 8 ppm or more and 75 ppm or less, and more preferably 10 ppm or more and 72 ppm or less, relative to 100% by mass of the PMA composition of this embodiment.

[0065] The above-mentioned content can be determined based on the methods described in the examples described later.

[0066] Regarding the aforementioned content, it can be adjusted to the above range, for example, by appropriately adding acetic acid and / or propionic acid after performing the adsorption treatment described later. Furthermore, the aforementioned content can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and dehydration treatment (e.g., treatment time, etc.).

[0067] (water)

[0068] The PMA composition of this embodiment contains water. From the viewpoint of storage stability, the water content in the PMA composition of this embodiment is 17 ppm or more and 250 ppm or less relative to 100% by mass, preferably 18 ppm or more and 200 ppm or less, and more preferably 20 ppm or more and 100 ppm or less.

[0069] The above-mentioned content can be determined based on the methods described in the examples described later.

[0070] Regarding the aforementioned content, it can be adjusted to the above range, for example, by appropriately adding water after performing the dehydration treatment described later. Furthermore, the aforementioned content can also be adjusted to the above range, for example, by appropriately changing the conditions of the dehydration treatment (e.g., treatment time).

[0071] (PM)

[0072] The PMA composition of this embodiment may also contain propylene glycol monomethyl ether (PM). Since PM tends to undergo intramolecular dehydration reactions in the presence of acid, it may affect the storage stability of the PMA composition; therefore, its content is preferably low. That is, from the viewpoint of storage stability, the PM content in the PMA composition of this embodiment is preferably 4.0 ppm or less, more preferably below the detection limit (2 ppm or less in GC analysis), relative to 100% by mass of the PMA composition of this embodiment.

[0073] The above-mentioned content can be determined based on the methods described in the examples described later.

[0074] Regarding the aforementioned content, it can be adjusted to the above range, for example, through azeotropic dehydration after esterification, followed by distillation purification, adsorption treatment, etc. In particular, the aforementioned content can be controlled by appropriately selecting an adsorbent in the adsorption treatment (step (c) described later). In this embodiment, as the adsorbent, various ion exchange resins such as KYOWAAD500 (registered trademark) manufactured by Kyowa Chemical Industry Co., Ltd., and ORLITE DS-6 manufactured by Organo Co., Ltd. can be used. For example, compared with the use of conventional inorganic synthetic adsorbents, the use of weakly basic ion exchange resins tends to further reduce the PM content, therefore, it is preferable to use weakly basic ion exchange resins such as ORLITE DS-6 manufactured by Organo Co., Ltd. to perform the adsorption treatment.

[0075] (ingredient A)

[0076] From the viewpoint of preserving stability, when the PMA composition of this embodiment is subjected to the following tests and then subjected to the above GC analysis, and the relative retention time of the peak of propylene glycol 1-monomethyl ether 2-acetic acid is set to 1.00, the area fraction of the peak appearing in the range of relative retention time of 0.64 or more and 0.72 or less (the substance corresponding to this peak is also referred to as "component A") is preferably 800 ppm or less, more preferably 700 ppm or less, and even more preferably 600 ppm or less.

[0077] (test)

[0078] The above-mentioned propylene glycol monomethyl ether acetate composition was heated to 80°C in a borosilicate glass container under a nitrogen atmosphere and maintained for 5 days.

[0079] The aforementioned area ratio can be determined based on the methods described in the embodiments described later.

[0080] Regarding the aforementioned area ratio, it can be adjusted to the above range, for example, by appropriately adding acetic acid, propionic acid, and / or water after performing the adsorption treatment and / or dehydration treatment described later. Furthermore, the aforementioned area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and / or dehydration treatment (e.g., treatment time, etc.).

[0081] (ethyl acetate)

[0082] From the viewpoint of preserving stability, when the PMA composition of this embodiment is subjected to the above-described test and then to the above-described GC analysis, the peak area of ​​ethyl acetate is preferably 120 ppm or less, more preferably 100 ppm or less, and even more preferably 70 ppm or less.

[0083] The aforementioned area ratio can be determined based on the methods described in the embodiments described later.

[0084] Regarding the aforementioned area ratio, it can be adjusted to the above range, for example, by appropriately adding acetic acid, propionic acid, and / or water after performing the adsorption treatment and / or dehydration treatment described later. Furthermore, the aforementioned area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and / or dehydration treatment (e.g., treatment time, etc.).

[0085] (Ingredient B)

[0086] From the viewpoint of preserving stability, when the PMA composition of this embodiment is subjected to the above-described test and then to the above-described GC analysis, the area fraction of the peak appearing in the range of 0.37 or more and 0.44 or less (the substance corresponding to this peak is also referred to as "component B") is preferably 70 ppm or less, more preferably 65 ppm or less, and even more preferably 60 ppm or less.

[0087] The aforementioned area ratio can be determined based on the methods described in the embodiments described later.

[0088] Regarding the aforementioned area ratio, it can be adjusted to the above range, for example, by appropriately adding acetic acid, propionic acid, and / or water after performing the adsorption treatment and / or dehydration treatment described later. Furthermore, the aforementioned area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and / or dehydration treatment (e.g., treatment time, etc.).

[0089] (2-Acetoxy-1-propanol)

[0090] From the viewpoint of preserving stability, when the PMA composition of this embodiment is subjected to the above-described test and then to the above-described GC analysis, the peak area of ​​2-acetoxy-1-propanol is preferably 240 ppm or less, more preferably 200 ppm or less, and even more preferably 150 ppm or less.

[0091] The aforementioned area ratio can be determined based on the methods described in the embodiments described later.

[0092] Regarding the aforementioned area ratio, it can be adjusted to the above range, for example, by appropriately adding acetic acid, propionic acid, and / or water after performing the adsorption treatment and / or dehydration treatment described later. Furthermore, the aforementioned area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and / or dehydration treatment (e.g., treatment time, etc.).

[0093] From the viewpoint of preserving stability, when the PMA composition of this embodiment is subjected to the above-described test and then to the above-described GC analysis, the peak area fraction of PGMEA is preferably 99.80% or more of the total peak area, more preferably 99.82% or more, and even more preferably 99.85% or more.

[0094] The aforementioned area ratio can be determined based on the methods described in the embodiments described later.

[0095] Regarding the aforementioned area ratio, it can be adjusted to the above range, for example, by appropriately adding acetic acid, propionic acid, and / or water after performing the adsorption treatment and / or dehydration treatment described later. Furthermore, the aforementioned area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and / or dehydration treatment (e.g., treatment time, etc.).

[0096] <Method for manufacturing PMA composition>

[0097] The method for manufacturing the PMA composition according to this embodiment is not particularly limited, but the following method (hereinafter also referred to as "method A") is preferred. Method A preferably includes: step (a) obtaining a first product containing PGMEA; step (b) distilling the first product to obtain a second product; step (c) subjecting the organic acid contained in the second product to adsorption treatment to obtain a third product; step (d) desalting the third product to obtain a fourth product; and step (e) subjecting the fourth product to dehydration treatment to obtain the PMA composition. Moreover, the amounts of acetic acid, propionic acid, and water in the PMA composition can be adjusted by steps (c) and (e), and may further include step (f) adding acetic acid, propionic acid, and / or water to the product obtained in step (e) to obtain the PMA composition.

[0098] (Step (a))

[0099] In step (a), a first product containing PGMEA is obtained. Step (a) may include operations based on conventionally known methods for manufacturing PGMEA. There are no particular limitations on the method for manufacturing PGMEA; for example, the method described in Chinese Patent Application Publication No. 1515537 may be cited. Specifically, it may be manufactured by performing a direct esterification reaction of PM with acetic acid, etc. The first product may also contain raw materials, catalysts, byproducts, etc., that may be used in the reaction for manufacturing PGMEA.

[0100] (Step (b))

[0101] In step (b), the first product is distilled to obtain the second product. The specific distillation operation is not particularly limited; for example, atmospheric distillation, vacuum distillation, etc., can be used, and the distillation can be repeated. This step removes raw materials, catalysts, byproducts, etc., that may be present in the first product in the reaction used to manufacture PGMEA. The distillation conditions are not particularly limited; for example, the conditions described in Chinese Patent Application Publication No. 1515537 can be used. Based on 100% by mass of the second product, the amounts of PM, acetic acid, propionic acid, and water that the second product may contain can exceed 4 ppm, 78 ppm, 30 ppm, and 250 ppm, respectively.

[0102] (Step (c))

[0103] In step (c), the second product is subjected to adsorption treatment to obtain the third product. The conditions for the adsorption treatment are preferably those that reduce the amount of acetic acid and propionic acid contained in the second product, but there are no particular limitations; for example, adsorption treatment using ORLITE DS-6 manufactured by Organo Corporation can be used. In this case, the amount of PM, acetic acid, and propionic acid that may be contained in the third product can be adjusted, for example, by adjusting the amount of ORLITE DS-6 used and the treatment time. The adsorbent such as ORLITE DS-6 used in the adsorption treatment can be removed by filtration using a PTFE (polytetrafluoroethylene) membrane filter or the like.

[0104] (Step (d))

[0105] In step (d), the third product is desalted to obtain the fourth product. The specific desalting procedure is not particularly limited; examples include flash evaporation or washing, and this process can be repeated. This step removes various amine salts and inorganic salts that may be present in the third product. The flash evaporation conditions are not particularly limited; for example, the third product can be supplied at a linear velocity (LV) of 55–65 m / h to a flash evaporator with a reduced pressure (absolute pressure within the system during distillation, the same below) of 2.5–3.5 kPa and heated to approximately 65–75°C.

[0106] (Step (e))

[0107] In step (e), the fourth product is subjected to a dehydration treatment to obtain the PMA composition. The dehydration treatment conditions are preferably those that reduce the amount of water contained in the fourth product, but are not particularly limited; for example, dehydration treatment using nitrogen bubbling can be used. At this time, the amount of water contained in the PMA composition can be adjusted, for example, by adjusting the treatment time.

[0108] (Step (f))

[0109] In step (f), acetic acid, propionic acid, and / or water may be added to the product obtained in step (e) to adjust the amounts of acetic acid, propionic acid, and / or water in the PMA composition. The amount of acetic acid, propionic acid, and / or water added is not particularly limited, and may be determined, for example, based on the difference between the desired content of acetic acid C1, propionic acid C2, and water C3 in the PMA composition and the content of acetic acid C1', propionic acid C2', and water C3' in the product obtained in step (e). Each content may be determined based on the methods described in the examples described later.

[0110] Example

[0111] The present embodiment will be described in further detail below based on examples. The present embodiment is not limited to these examples.

[0112] [Example 1]

[0113] (Step (a))

[0114] The first product containing PGMEA was synthesized by referring to the method described in Chinese Patent Application Publication No. 1515537. That is, the first product containing PGMEA was obtained by direct esterification reaction of PM with acetic acid.

[0115] (Step (b))

[0116] Next, the first product containing PGMEA is introduced into a distillation column for atmospheric distillation. That is, the reflux ratio is set to 1 to 9, and unreacted raw materials are first removed by distillation, followed by the recovery of the component containing PGMEA.

[0117] Next, the PGMEA-containing component obtained by atmospheric distillation was introduced into a distillation column for vacuum distillation. Specifically, the vacuum level in the distillation column was set to 21.3 kPa, the temperature was controlled below 110°C, and the reflux ratio was set to 1–6. The component at the top of the column (temperature 98–100°C) was recovered as the second product. Based on 100% mass of the second product, the amounts of PM, acetic acid, propionic acid, and water in the obtained second product were below the detection limit (below the detection limit in GC analysis), 90 ppm, 50 ppm, and 300 ppm, respectively.

[0118] The contents of PM, acetic acid, propionic acid, and water in the second product, and the contents of PGMEA, PM, acetic acid, propionic acid, and water in the PMA composition of Example 1 described later, were confirmed by the following method. Specifically, the water content was determined using a Karl Fischer moisture analyzer (product name "AQ-2200A", manufactured by Hiranuma Co., Ltd., Karl Fischer electrostatic titration method). The contents of PGMEA, PM, acetic acid, and propionic acid were determined by GC analysis under the following conditions.

[0119] (Gas Chromatography Analysis)

[0120] Analysis device: Nexis GC-2030 manufactured by Shimadzu Corporation

[0121] Analytical column: DB-WAX manufactured by Agilent Technologies (stationary phase: polyethylene glycol, length 30m × inner diameter 0.25mm × film thickness 0.25μm).

[0122] Heating conditions: Hold at 50℃ for 10 minutes, then increase to 250℃ at a rate of 5℃ / minute.

[0123] Sample introduction temperature: 250℃

[0124] Carrier gas: Nitrogen

[0125] Column gas flow rate: 1.0 mL / min

[0126] Detector and detection temperature: Flame ionization detector, 250℃

[0127] Control mode: Column flow

[0128] Flow split ratio: 50:1

[0129] Injection volume: 2.0 μL

[0130] In the above GC analysis, the PGMEA content was calculated as the percentage of the PGMEA peak area relative to the total peak area of ​​the spectrum obtained from the GC analysis. The PM content was calculated as the percentage of the PM peak area relative to the total peak area of ​​the spectrum obtained from the GC analysis. Furthermore, the contents of acetic acid and propionic acid were calculated by GC analysis using the absolute calibration curve method.

[0131] (Step (c))

[0132] Add 5.0 vol% of ORLITE DS-6 manufactured by Organo Co., Ltd. to the second product (100 vol%) obtained above, and stir for 30 minutes to adsorb and remove acetic acid and propionic acid. Filter the product using a PTFE membrane filter manufactured by ADVANTEC (model: T020A047A, pore size: 0.20 μm) to obtain the third product.

[0133] (Step (d))

[0134] Next, the third product is introduced into a distillation column for flash distillation. That is, the third product is fed at a linear velocity (LV) of 59 m / h into a flash tank with a depressurization of 3 kPa and heated to about 70°C, and the product obtained by distilling off from the top of the flash tank (90% by mass relative to 100% of the third product) is taken as the fourth product.

[0135] (Step (e))

[0136] Nitrogen gas, passing through a Kinoshita-type spherical filter (model: 501G-1, filter diameter: 10 mm, filter pore size: 100-120 μm) manufactured by Kinoshita Rika Kogyo, was bubbled into the fourth product at a rate of 3-5 L / min for 110 minutes to dehydrate it, yielding the PMA composition of Example 1. The obtained PMA composition was subjected to GC analysis and moisture analysis under the same conditions as described above. Based on 100% by mass, the amounts of PGMEA, PM, acetic acid, propionic acid, and water in the PMA composition were 99.966% by area, below the detection limit, 10 ppm, 5 ppm, and 20 ppm, respectively. Details of the analytical results are shown in Table 1.

[0137] The amounts of PGMEA, PM, acetic acid, propionic acid, and water in the PMA compositions are also confirmed in the following examples and comparative examples as described above.

[0138] Next, the PMA composition was subjected to the following test. The PMA composition was placed in a 110 mL borosilicate glass container, sealed with nitrogen, and heated using a thermostat (product name "ST-110B1", manufactured by ESPEC) at 80°C for 5 days.

[0139] The PMA composition after the above experiment was subjected to GC analysis under the above conditions.

[0140] Comparing GC spectrum A obtained before the above experiment with GC spectrum B obtained after the above experiment, substances with a peak area ratio of less than 5 ppm in spectrum A and a peak area ratio of more than 5 ppm in spectrum B were considered to have a significant impact on the storage stability of the PMA composition, and their amounts were evaluated. Specifically, in GC spectrum B, when the relative retention time of the propylene glycol 1-monomethyl ether 2-acetic acid ester peak was set to 1.00, the area ratios of the peaks appearing within the relative retention time range of 0.64–0.72 and 0.37–0.44 were 567.6 ppm and 53.1 ppm, respectively. Furthermore, in GC spectrum B, the area ratios of the ethyl acetate peak and the 2-acetoxy-1-propanol peak were 51.7 ppm and 126.8 ppm, respectively. Furthermore, in GC spectrum A, the peaks corresponding to propylene glycol monomethyl ether (PM) with relative retention times in the range of 0.62–0.64 are below the detection limit (below 2 ppm). Details of the analytical results are shown in Table 1.

[0141] (Example 2)

[0142] Except for adding 4.0 vol% of ORLITE DS-6 manufactured by Organo Co., Ltd. to the second product (100 vol%) in step (c) of Example 1, and bubbling nitrogen into the fourth product in step (e) for 105 minutes at the above-described supply rate, the same procedure as in Example 1 was followed to obtain the PMA composition of Example 2. This PMA composition was subjected to the same tests as in Example 1 and then analyzed by the same gas chromatography method as in Example 1. Details of the analytical results are shown in Table 1.

[0143] (Example 3)

[0144] Except for adding 5.1 vol% of ORLITE DS-6 manufactured by Organo Co., Ltd. to the second product (100 vol%) in step (c) of Example 1, and bubbling nitrogen into the fourth product in step (e) at the above-described supply rate for 90 minutes, the procedure was the same as in Example 1 to obtain the PMA composition of Example 3. This PMA composition was subjected to the same tests as in Example 1 and then analyzed by the same gas chromatography method as in Example 1. Details of the analytical results are shown in Table 1.

[0145] (Example 4)

[0146] Except for adding 3.4 vol% of ORLITE DS-6 manufactured by Organo Co., Ltd. to the second product (100 vol%) in step (c) of Example 1, and bubbling nitrogen into the fourth product in step (e) at the above-described supply rate for 80 minutes, the procedure was the same as in Example 1 to obtain the PMA composition of Example 4. This PMA composition was subjected to the same tests as in Example 1 and then analyzed by the same gas chromatography method as in Example 1. Details of the analytical results are shown in Table 1.

[0147] (Example 5)

[0148] Except for adding 2.5 vol% of ORLITE DS-6 manufactured by Organo Co., Ltd. to the second product (100 vol%) in step (c) of Example 1, and bubbling nitrogen into the fourth product in step (e) at the above-described supply rate for 80 minutes, the procedure was the same as in Example 1 to obtain the PMA composition of Example 5. This PMA composition was subjected to the same tests as in Example 1 and then analyzed by the same gas chromatography method as in Example 1. Details of the analytical results are shown in Table 1.

[0149] (Comparative Example 1)

[0150] Except for adding 5.0 vol% of ORLITE DS-6 manufactured by Organo Co., Ltd. to the second product (100 vol%) in step (c) of Example 1, and bubbling nitrogen into the fourth product in step (e) for 115 minutes at the above-described supply rate, the same procedure as in Example 1 was followed to obtain the PMA composition of Comparative Example 1. This PMA composition was subjected to the same tests as in Example 1 and then analyzed by the same gas chromatography method as in Example 1. Details of the analytical results are shown in Table 1.

[0151]

Claims

1. A propylene glycol monomethyl ether acetate composition, comprising propylene glycol 1-monomethyl ether 2-acetate, acetic acid, propionic acid, and water, wherein, The content of propionic acid is 2 ppm or more and 30 ppm or less relative to 100% by mass of the propylene glycol monomethyl ether acetate composition. Relative to 100% by mass of the propylene glycol monomethyl ether acetate composition, the sum of the content of acetic acid and propionic acid is 5 ppm or more and 80 ppm or less. The water content, relative to 100% by mass of the propylene glycol monomethyl ether acetate composition, is 17 ppm or more and 250 ppm or less. The contents of acetic acid and propionic acid were determined by gas chromatography and calculated using an absolute calibration curve method, and the contents of water were determined by Karl Fischer titration.

2. The propylene glycol monomethyl ether acetate composition according to claim 1, wherein, The content of propylene glycol monomethyl ether relative to 100% by mass of the propylene glycol monomethyl ether acetate composition is 4.0 ppm or less. The content of propylene glycol monomethyl ether is a value calculated as the percentage of the peak area of ​​propylene glycol monomethyl ether relative to the total peak area of ​​the spectrum obtained by gas chromatography analysis.

3. The propylene glycol monomethyl ether acetate composition according to claim 1 or 2, wherein, The water content is 20 ppm or more and 100 ppm or less relative to 100% by mass of the propylene glycol monomethyl ether acetate composition, and the water content is a value determined by Karl Fischer electrostatic titration.

4. The propylene glycol monomethyl ether acetate composition according to claim 1 or 2, wherein, When the propylene glycol monomethyl ether acetate composition is subjected to the following tests and then analyzed by gas chromatography under the following conditions, with the relative retention time of the propylene glycol 1-monomethyl ether 2-acetate peak set to 1.00, the peak area in the range of 0.64 to 0.72 is less than 800 ppm. test: The propylene glycol monomethyl ether acetate composition was heated to 80°C in a borosilicate glass container under a nitrogen atmosphere and maintained for 5 days. Conditions for gas chromatography analysis: Analytical column: A column with polyethylene glycol as the stationary phase, 30m in length × 0.25mm in inner diameter × 0.25μm in film thickness; Heating conditions: Hold at 50℃ for 10 minutes, then increase the temperature to 250℃ at a rate of 5℃ / minute; Sample introduction temperature: 250℃; Carrier gas: Nitrogen; Column gas flow rate: 1.0 mL / min; Detector and detection temperature: Hydrogen flame ionization detector, 250℃; Control mode: Column flow rate; Flow split ratio: 50:1; Injection volume: 2.0 μL.

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