Propylene glycol monomethyl ether acetate composition

Abstract

Propylene glycol 1-monomethyl ether 2-acetate, Acetic acid, Propionic acid, Water, A propylene glycol monomethyl ether acetate composition comprising: The content of the propionic acid is 2 ppm or more and 30 ppm or less based on 100% by 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% by mass of the propylene glycol monomethyl ether acetate composition; A propylene glycol monomethyl ether acetate composition, wherein the water content is 17 ppm or more and 250 ppm or less, based on 100 mass % of the propylene glycol monomethyl ether acetate composition.

Description

[Technical field]

[0001] The present invention relates to a propylene glycol monomethyl ether acetate composition. [Background technology]

[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 carrying out a direct esterification reaction between propylene glycol monomethyl ether (hereinafter also referred to as "PM") and acetic acid under certain conditions (for example, see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] China Patent Application Publication No. 1515537 Summary of the Invention [Problem to be solved by the invention]

[0004] When PMA obtained by the method described in Patent Document 1 was stored for a long period of time and its composition was confirmed, it was found that the purity of the PMA tends to decrease.

[0005] The present invention has been made in consideration of the above points, and an object of the present invention is to provide a propylene glycol monomethyl ether acetate composition having excellent storage stability. [Means for solving the problem]

[0006] The present inventors have found that a propylene glycol monomethyl ether acetate composition containing specific components can solve the above problems, and have completed the present invention.

[0007] That is, the present invention includes the following aspects. [1] Propylene glycol 1-monomethyl ether 2-acetate, Acetic acid, Propionic acid, Water, A propylene glycol monomethyl ether acetate composition comprising: The content of the propionic acid is 2 ppm or more and 30 ppm or less based on 100% by 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% by mass of the propylene glycol monomethyl ether acetate composition; A propylene glycol monomethyl ether acetate composition, wherein the water content is 17 ppm or more and 250 ppm or less, based on 100 mass % of the propylene glycol monomethyl ether acetate composition. [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 based on 100% by mass of the propylene glycol monomethyl ether acetate composition. [3] The propylene glycol monomethyl ether acetate composition according to [1] or [2], wherein the water content is 20 ppm or more and 100 ppm or less, based on 100 mass% of the propylene glycol monomethyl ether acetate composition. [4] The propylene glycol monomethyl ether acetate composition according to any one of [1] to [3], wherein when the propylene glycol monomethyl ether acetate composition is subjected to the following tests and then subjected to gas chromatography analysis under the following conditions, when the relative retention time of the peak of propylene glycol 1-monomethyl ether 2-acetate is taken as 1.00, the area ratio of a peak appearing in a relative retention time range of 0.64 to 0.72 is 800 ppm or less. (test) The propylene glycol monomethyl ether acetate composition is heated to 80° C. in a borosilicate glass vessel under a nitrogen atmosphere and maintained for 5 days. (Gas chromatographic analysis conditions) Analytical column: A column with a stationary phase of polyethylene glycol, length 30 m, inner diameter 0.25 mm, and film thickness 0.25 μm Heating conditions: After holding at 50°C for 10 minutes, heat to 250°C at 5°C / min 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 Split ratio: 50:1 Injection volume: 2.0μL Effect of the Invention

[0008] According to the present invention, a propylene glycol monomethyl ether acetate composition having excellent storage stability can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, an embodiment for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0010] <Propylene glycol monomethyl ether acetate composition> The propylene glycol monomethyl ether acetate composition (hereinafter also referred to as "PMA composition") of this embodiment 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, in which the content of the propionic acid is 2 ppm or more and 30 ppm or less with respect to 100% by 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% by 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% by mass of the propylene glycol monomethyl ether acetate composition. The PMA composition of this embodiment has such a constitution and therefore has excellent storage stability.

[0011] The reason why the PMA composition of the present embodiment has excellent storage stability is not necessarily clear, and although it is not intended to limit the reason, it is presumed to be as follows. In the long-term storage of the propylene glycol monomethyl ether acetate composition, the decomposition of PGMEA and the generation of impurities are considered to be one of the factors affecting the storage stability. For example, hydrolysis can be cited as a cause of the decomposition of a carboxylic acid ester such as PGMEA. In general, when an acid and water are present, a carboxylic acid ester is hydrolyzed to a carboxylic acid and an alcohol. It is also considered that when the acid content is high, the carboxylic acid ester tends to be hydrolyzed more. However, in the PMA composition of the present embodiment, since the propionic acid content, the sum of the acetic acid content and the propionic acid content, and the water content are within the above ranges, transesterification between alcohols that may be generated by hydrolysis of PGMEA and the acetyl group of PGMEA is suppressed, and as a result, hydrolysis of PGMEA is suppressed, unlike the above-mentioned tendency. However, the above is merely one possible reason why the PMA composition of the present embodiment has excellent storage stability, and the mechanism of action of the present embodiment is not limited thereto.

[0012] The applications of the PMA composition of the present embodiment are not particularly limited, and can be used for industrial applications such as inks, thinners, medical and agricultural chemicals, plasticizers, surfactants, polymeric materials, lubricants, adhesives, detergents, electronic materials, and paints. The electronic material is not particularly limited, but examples thereof include liquid crystal displays (LCDs), semiconductor devices, etc. Since the PMA composition of the present embodiment has excellent storage stability, it is preferably used in the manufacture of semiconductor devices. Specific examples of applications relating to the manufacture of semiconductor devices include, but are not limited to, cleaning solutions (e.g., treatment solutions for cleaning the surface of a substrate after resist stripping), pre-wetting solutions (e.g., treatment solutions used before resist coating to reduce the consumption of resist solvents), resist solvents (e.g., treatment solutions for dissolving photosensitizers and resins), developing solutions (e.g., treatment solutions for removing soluble resins after exposure of a negative resist), stripping solutions (e.g., treatment solutions used to remove hardened resist after etching), etc. From the viewpoint of preventing product defects in the manufacture of semiconductor devices, the PMA composition of this embodiment is preferably used as a resist solvent, a pre-wetting solution, a solvent for edge rinse (rinse for removing resist from the outer periphery of a wafer) and back rinse (rinse for removing resist from the back surface of a wafer) used during resist coating, a developing solution used during negative resist development, a rinsing solution used during rinsing after development of a negative resist, a cleaning solution or rinsing solution used for removing resist after etching, etc.

[0013] (Propylene glycol 1-monomethyl ether 2-acetate) The propylene glycol 1-monomethyl ether 2-acetate in the PMA composition of the present embodiment can be identified and quantified, for example, by the following gas chromatography (hereinafter also referred to as "GC") analysis. (Gas Chromatography Analysis) Analytical column: A column with a stationary phase of polyethylene glycol, length 30 m, inner diameter 0.25 mm, and film thickness 0.25 μm Heating conditions: After holding at 50°C for 10 minutes, heat to 250°C at 5°C / min 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 Split ratio: 50:1 Injection volume: 2.0μL The content of PGMEA in the PMA composition of the present embodiment can be appropriately determined according to the application of the PMA composition of the present embodiment, and is not particularly limited. From the viewpoint of using the composition in an application requiring high purity, the peak area ratio to the total peak area of ​​the chart obtained as a result of GC analysis is preferably 99.94% or more, more preferably 99.95% or more, and even more preferably 99.96% or more. In this embodiment, the "total peak area" means the total area of ​​all peaks appearing in the chart obtained as a result of GC analysis. In this embodiment, "all peaks" can be specified as meaning all peaks that appear when the analysis is continued and stopped from the relative retention time of 0.14 to 2.95, when the relative retention time of the peak of PGMEA is set to 1.00.

[0014] (Acetic Acid) The PMA composition of the present embodiment contains acetic acid. From the viewpoint of storage stability, the content of acetic acid in the PMA composition of the present 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, based on 100% by mass of the PMA composition of the present embodiment. The above content can be measured based on the method described in the examples below. The content can be adjusted to the above range, for example, by appropriately adding acetic acid after performing the adsorption treatment described below. The content can also be adjusted to the above range, for example, by appropriately changing the conditions (e.g., treatment time, etc.) of the adsorption treatment and the dehydration treatment.

[0015] (Propionic Acid) The PMA composition of the present embodiment contains propionic acid. From the viewpoint of storage stability, the content of propionic acid in the PMA composition of the present 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 mass% of the PMA composition of the present embodiment. The above content can be measured based on the method described in the examples below. The content can be adjusted to the above range, for example, by appropriately adding propionic acid after performing the adsorption treatment described below. The content can also be adjusted to the above range, for example, by appropriately changing the conditions (e.g., treatment time, etc.) of the adsorption treatment and the dehydration treatment.

[0016] (Total of acetic acid and propionic acid content) In this embodiment, from the viewpoint of storage stability, the sum of the contents of acetic acid and propionic acid in the PMA composition of this embodiment is, relative to 100 mass% of the PMA composition of this embodiment, 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. The above content can be measured based on the method described in the examples below. The above content can be adjusted to the above range, for example, by appropriately adding acetic acid and / or propionic acid after performing the adsorption treatment described below. The above content can also be adjusted to the above range, for example, by appropriately changing the conditions of the adsorption treatment and the dehydration treatment (for example, the treatment time, etc.).

[0017] (water) The PMA composition of the present embodiment contains water. From the viewpoint of storage stability, the content of water in the PMA composition of the present embodiment is from 17 ppm to 250 ppm, preferably from 18 ppm to 200 ppm, and more preferably from 20 ppm to 100 ppm, relative to 100 mass% of the PMA composition of the present embodiment. The above content can be measured based on the method described in the examples below. The content can be adjusted to the above range, for example, by adding water appropriately after carrying out a dehydration treatment described later, etc. The content can also be adjusted to the above range, for example, by appropriately changing the conditions of the dehydration treatment (for example, the treatment time, etc.).

[0018] (PM) The PMA composition of the present embodiment may contain propylene glycol monomethyl ether (PM). PM tends to undergo intramolecular dehydration reactions in the presence of acid, which may affect the storage stability of the PMA composition, so its content is preferably low. That is, from the viewpoint of storage stability, the content of PM in the PMA composition of the present embodiment is preferably 4.0 ppm or less relative to 100% by mass of the PMA composition of the present embodiment, and more preferably below the detection limit (2 ppm or less in GC analysis). The above content can be measured based on the method described in the examples below. The content can be adjusted to the above-mentioned range, for example, by azeotropic dehydration after esterification, subsequent distillation purification, adsorption treatment, etc. In particular, in the adsorption treatment (step (c) described below), the content can be controlled by appropriately selecting the adsorbent. In this embodiment, various ion exchange resins such as Kyoward 500 (registered trademark) manufactured by Kyowa Chemical Industry Co., Ltd. and ORLITE DS-6 manufactured by Organo Corporation can be used as the adsorbent. However, since the use of a weakly basic ion exchange resin tends to reduce the amount of PM more than the use of a general inorganic synthetic adsorbent, it is preferable to carry out the adsorption treatment using a weakly basic ion exchange resin such as ORLITE DS-6 manufactured by Organo Corporation.

[0019] (Component A) From the viewpoint of storage stability, when the PMA composition of the present embodiment is subjected to the following test and then to the above-mentioned GC analysis, when the relative retention time of the peak of propylene glycol 1-monomethyl ether 2-acetate is taken as 1.00, the area ratio of a peak appearing in the relative retention time range 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. (test) The propylene glycol monomethyl ether acetate composition is heated to 80° C. in a borosilicate glass vessel under a nitrogen atmosphere and maintained for 5 days. The area ratio can be measured based on the method described in the examples below. The area ratio can be adjusted to the above-mentioned range, for example, by appropriately adding acetic acid, propionic acid and / or water after performing the adsorption treatment and / or dehydration treatment described below. The area ratio can also be adjusted to the above-mentioned range, for example, by appropriately changing the conditions of the adsorption treatment and / or dehydration treatment (for example, the treatment time, etc.).

[0020] (Ethyl Acetate) From the viewpoint of storage stability, when the PMA composition of the present embodiment is subjected to the above-mentioned test and then to the above-mentioned GC analysis, the area ratio of the peak of ethyl acetate is preferably 120 ppm or less, more preferably 100 ppm or less, and even more preferably 70 ppm or less. The area ratio can be measured based on the method described in the examples below. The area ratio can be adjusted to the above-mentioned range, for example, by appropriately adding acetic acid, propionic acid and / or water after performing the adsorption treatment and / or dehydration treatment described below. The area ratio can also be adjusted to the above-mentioned range, for example, by appropriately changing the conditions of the adsorption treatment and / or dehydration treatment (for example, the treatment time, etc.).

[0021] (Component B) From the viewpoint of storage stability, when the PMA composition of the present embodiment is subjected to the above-mentioned test and then to the above-mentioned GC analysis, when the relative retention time of the peak of propylene glycol 1-monomethyl ether 2-acetate is taken as 1.00, the area ratio of a peak appearing in the relative retention time range of 0.37 to 0.44 (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. The area ratio can be measured based on the method described in the examples below. The area ratio can be adjusted to the above-mentioned range, for example, by appropriately adding acetic acid, propionic acid and / or water after performing the adsorption treatment and / or dehydration treatment described below. The area ratio can also be adjusted to the above-mentioned range, for example, by appropriately changing the conditions of the adsorption treatment and / or dehydration treatment (for example, the treatment time, etc.).

[0022] (2-Acetoxy-1-propanol) From the perspective of storage stability, when the PMA composition of this embodiment is subjected to the aforementioned tests and then to the aforementioned GC analysis, the area ratio of the peak 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. The above area ratio can be measured based on the method described in the examples below. The above area ratio can be adjusted to the above-mentioned range, for example, by appropriately adding acetic acid, propionic acid, and / or water after performing the adsorption treatment and / or dehydration treatment described below. Also, the above area ratio can be adjusted to the above-mentioned range, for example, by appropriately changing the conditions (such as treatment time) of the adsorption treatment and / or dehydration treatment.

[0023] From the perspective of storage stability, when the PMA composition of this embodiment is subjected to the aforementioned tests and then to the aforementioned GC analysis, the area ratio of the peak 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. The above area ratio can be measured based on the method described in the examples below. The above area ratio can be adjusted to the above-mentioned range, for example, by appropriately adding acetic acid, propionic acid, and / or water after performing the adsorption treatment and / or dehydration treatment described below. Also, the above area ratio can be adjusted to the above-mentioned range, for example, by appropriately changing the conditions (such as treatment time) of the adsorption treatment and / or dehydration treatment.

[0024] <Method for manufacturing PMA composition> The method for producing the PMA composition of the present embodiment is not particularly limited, but the following method (hereinafter also referred to as "Production Method A") is preferred. Production Method A preferably includes the steps of (a) obtaining a first product containing PGMEA, (b) distilling the first product to obtain a second product, (c) subjecting the organic acid contained in the second product to an adsorption treatment to obtain a third product, (d) desalting the third product to obtain a fourth product, and (e) dehydrating the fourth product to obtain a PMA composition. The amounts of acetic acid, propionic acid, and water in the PMA composition can be adjusted by steps (c) and (e), but the method may further include a step (f) of adding acetic acid, propionic acid, and / or water to the product obtained through step (e) to obtain a PMA composition.

[0025] (Step (a)) In step (a), a first product containing PGMEA is obtained. Step (a) can include an operation of producing PGMEA based on a conventionally known method. The method for producing PGMEA is not particularly limited, but for example, the method described in Chinese Patent Application Publication No. 1515537 can be mentioned. Specifically, PGMEA can be produced by carrying out a direct esterification reaction between PM and acetic acid. The first product may contain raw materials, catalysts, by-products, etc. that can be used in the reaction for producing PGMEA.

[0026] (Step (b)) In step (b), the first product is distilled to obtain a second product. The specific operation of the distillation is not particularly limited, and examples thereof include atmospheric distillation and reduced pressure distillation, and such distillation may be performed repeatedly. In this step, raw materials, catalysts, by-products, etc. that may be contained in the first product and may be used in the reaction for producing PGMEA can be removed. The conditions of the distillation are not particularly limited, and the distillation can be performed with reference to the conditions described in Chinese Patent Application Publication No. 1515537, for example. The amounts of PM, acetic acid, propionic acid, and water that may be contained in the second product may be more than 4 ppm, more than 78 ppm, more than 30 ppm, and more than 250 ppm, respectively, based on 100% by mass of the second product.

[0027] (Process (c)) In step (c), the second product is subjected to an adsorption treatment to obtain a third product. The conditions of the adsorption treatment are preferably conditions that can reduce the amount of acetic acid and propionic acid contained in the second product, and are not particularly limited, but examples thereof include subjecting the second product to an adsorption treatment using ORLITE DS-6 manufactured by Organo Corporation. In this case, for example, the amount of ORLITE DS-6 used and the treatment time can be adjusted to adjust the amount of PM, acetic acid, and propionic acid that can be contained in the third product. 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.

[0028] (Step (d)) In step (d), the third product is desalted to obtain a fourth product. The specific operation of the desalting treatment is not particularly limited, and examples thereof include flash distillation or water washing, and such treatments may be repeated. In this step, various amine salts and inorganic salts that may be contained in the third product can be removed. The conditions for flash distillation are not particularly limited, and the third product can be supplied to a flash drum heated to about 65 to 75°C at a reduced pressure (absolute pressure in the system during distillation; the same applies below) of 2.5 to 3.5 kPa at a linear velocity (LV) of 55 to 65 m / Hr.

[0029] (Step (e)) In step (e), the fourth product is subjected to a dehydration treatment to obtain a PMA composition. The conditions of the dehydration treatment are preferably conditions that can reduce the amount of water contained in the fourth product, and are not particularly limited, but examples thereof include dehydration treatment by nitrogen bubbling. At this time, the amount of water contained in the PMA composition can be adjusted, for example, by adjusting the treatment time, etc.

[0030] (Step (f)) In step (f), the amount of acetic acid, propionic acid and / or water in the PMA composition can be adjusted by adding acetic acid, propionic acid and / or water to the product obtained through step (e). The amount of acetic acid, propionic acid and / or water to be added is not particularly limited, but can be determined, for example, based on the difference between the content C1 of acetic acid, the content C2 of propionic acid and the content C3 of water in the desired PMA composition and the content C1' of acetic acid, the content C2' of propionic acid and the content C3' of water in the product obtained through step (e). Each content can be measured based on the method described in the Examples below. EXAMPLES

[0031] The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to these examples.

[0032] [Example 1] (Step (a)) The first product containing PGMEA was synthesized by referring to the method described in Chinese Patent Publication No. 1515537. That is, the first product containing PGMEA was obtained by direct esterification reaction of PM with acetic acid.

[0033] (Step (b)) Next, the first product containing PGMEA was introduced into a distillation column and distilled under atmospheric pressure. That is, the reflux ratio was set to 1 to 9, and first, unreacted raw materials and the like were distilled off, and then a fraction containing PGMEA was recovered.

[0034] Next, the fraction containing PGMEA obtained by atmospheric distillation was introduced into a distillation column, and reduced pressure distillation was carried out. That is, the degree of vacuum in the distillation column was set to 21.3 kPa, the temperature in the distillation column was controlled to be 110°C or less, the reflux ratio was set to 1 to 6, and the fraction at the top of the column (temperature 98 to 100°C) was recovered as the second product. The amounts of PM, acetic acid, propionic acid, and water contained 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, with the second product being 100% by mass.

[0035] 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. That is, the water content was measured with a Karl Fischer moisture meter (product name "AQ-2200A", Hiranuma Corporation, Karl Fischer coulometric titration method). The contents of PGMEA, PM, acetic acid and propionic acid were measured by GC analysis under the following conditions. (Gas Chromatography Analysis) Analyzer: Shimadzu Nexis GC-2030 Analytical column: Agilent Technologies DB-WAX (column with polyethylene glycol as stationary phase, length 30 m × inner diameter 0.25 mm × film thickness 0.25 μm) Heating conditions: After holding at 50°C for 10 minutes, heat to 250°C at 5°C / min 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 Split ratio: 50:1 Injection volume: 2.0μL In the above GC analysis, the content of PGMEA was calculated as the percentage of the peak area of ​​PGMEA relative to the total peak area of ​​the chart obtained as a result of GC analysis. The content of PM was calculated as the percentage of the peak area of ​​PM relative to the total peak area of ​​the chart obtained as a result of GC analysis. The contents of acetic acid and propionic acid were calculated by the absolute calibration curve method using GC analysis.

[0036] (Process (c)) To the second product (100% by volume) obtained above, 5.0% by volume of ORLITE DS-6 manufactured by Organo Corporation was added and stirred for 30 minutes to adsorb and remove acetic acid and propionic acid. The mixture was filtered with a PTFE membrane filter (model: T020A047A, pore size: 0.20 μm) manufactured by ADVANTEC to obtain a third product.

[0037] (Step (d)) Next, the third product was introduced into a distillation column and flash distillation was carried out. That is, the third product was fed into a flash drum heated to about 70° C. under a reduced pressure of 3 kPa at a linear velocity (LV) of 59 m / Hr, and 90 mass% (relative to 100 mass% of the third product) was distilled from the top of the flash drum to obtain a fourth product.

[0038] (Step (e)) Nitrogen passed through a Kinoshita ball filter (model number: 501G-1, filter diameter: 10 mm, filter hole: 100-120 μm) manufactured by Kinoshita Rika Kogyo Co., Ltd. was bubbled into the fourth product at 3-5 L / min for 110 minutes for dehydration treatment to obtain the PMA composition of Example 1. The obtained PMA composition was subjected to GC analysis and moisture analysis under the same conditions as above. The amounts of PGMEA, PM, acetic acid, propionic acid and water contained in the PMA composition were 99.966 area %, below the detection limit, 10 ppm, 5 ppm and 20 ppm, respectively, assuming the PMA composition to be 100 mass %. Details of the analysis results are shown in Table 1. In the following Examples and Comparative Examples, the amounts of PGMEA, PM, acetic acid, propionic acid, and water in the PMA composition were confirmed in the same manner as above.

[0039] The PMA composition was then subjected to the following test: the PMA composition was placed in a 110 mL borosilicate glass container, nitrogen was enclosed, the container was sealed, and the container was heated in an incubator (product name "ST-110B1", manufactured by ESPEC) and maintained at 80°C for 5 days. The PMA composition after the above test was subjected to GC analysis under the above conditions.

[0040] The GC chart A obtained by the GC analysis before the above test was compared with the GC chart B obtained by the GC analysis after the above test, and the substances that had a peak area ratio of less than 5 ppm in the chart A and a peak area ratio of 5 ppm or more in the chart B were determined to be substances that have a large effect on the storage stability of the PMA composition, and the amounts of these substances were evaluated. That is, when the relative retention time of the peak of propylene glycol 1-monomethyl ether 2-acetate in the GC chart B is set to 1.00, the area ratios of the peaks appearing at relative retention times of 0.64 to 0.72 and the area ratios of the peaks appearing at relative retention times of 0.37 to 0.44 were 567.6 area ppm and 53.1 area ppm, respectively. In addition, the area ratios of the peaks of ethyl acetate and 2-acetoxy-1-propanol in the GC chart B were 51.7 area ppm and 126.8 area ppm, respectively. In addition, in GC chart A, the peak in the range of relative retention time 0.62 to 0.64 corresponding to propylene glycol monomethyl ether (PM) was below the detection limit (2 ppm or less). Details of the analysis results are shown in Table 1.

[0041] Example 2 The PMA composition of Example 2 was obtained in the same manner as in Example 1, except that 4.0 vol. % of ORLITE DS-6 manufactured by Organo Corporation was added to the second product (100 vol. %) in step (c) in Example 1, and nitrogen was bubbled for 105 minutes at the aforementioned supply rate into the fourth product in step (e). The PMA composition was subjected to the same tests as in Example 1, and then subjected to the same gas chromatography analysis as in Example 1. Details of the analysis results are shown in Table 1.

[0042] Example 3 The PMA composition of Example 3 was obtained in the same manner as in Example 1, except that 5.1 volume % of ORLITE DS-6 manufactured by Organo Corporation was added to the second product (100 volume %) of step (c) in Example 1, and nitrogen was bubbled for 90 minutes at the aforementioned supply rate into the fourth product of step (e). The PMA composition was subjected to the same tests as in Example 1, and then subjected to the same gas chromatography analysis as in Example 1. Details of the analysis results are shown in Table 1.

[0043] Example 4 The PMA composition of Example 4 was obtained in the same manner as in Example 1, except that 3.4 vol. % of ORLITE DS-6 manufactured by Organo Corporation was added to the second product (100 vol. %) in step (c) in Example 1, and nitrogen was bubbled for 80 minutes at the aforementioned supply rate into the fourth product in step (e). The PMA composition was subjected to the same tests as in Example 1, and then subjected to the same gas chromatography analysis as in Example 1. Details of the analysis results are shown in Table 1.

[0044] Example 5 The PMA composition of Example 5 was obtained in the same manner as in Example 1, except that 2.5% by volume of ORLITE DS-6 manufactured by Organo Corporation was added to the second product (100% by volume) in step (c) in Example 1, and nitrogen was bubbled for 80 minutes at the aforementioned supply rate into the fourth product in step (e). The PMA composition was subjected to the same tests as in Example 1, and then subjected to the same gas chromatography analysis as in Example 1. Details of the analysis results are shown in Table 1.

[0045] Comparative Example 1 A PMA composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that 5.0 vol. % of ORLITE DS-6 manufactured by Organo Corporation was added to the second product (100 vol. %) in step (c) in Example 1, and nitrogen was bubbled for 115 minutes at the aforementioned supply rate into the fourth product in step (e). The PMA composition was subjected to the same tests as in Example 1, and then subjected to the same gas chromatography analysis as in Example 1. Details of the analysis results are shown in Table 1.

[0046]

Table 1

Claims

1. propylene glycol 1-monomethyl ether 2-acetate, Acetic acid, Propionic acid, Water, A propylene glycol monomethyl ether acetate composition comprising: The content of the propionic acid is 2 ppm or more and 30 ppm or less based on 100% by 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 based on 100% by mass of the propylene glycol monomethyl ether acetate composition; A propylene glycol monomethyl ether acetate composition, wherein the water content is 17 ppm or more and 250 ppm or less, based on 100 mass% of the propylene glycol monomethyl ether acetate composition.

2. 2. The propylene glycol monomethyl ether acetate composition according to claim 1, wherein the content of propylene glycol monomethyl ether is 4.0 ppm or less based on 100% by mass of the propylene glycol monomethyl ether acetate composition.

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, based on 100 mass% of the propylene glycol monomethyl ether acetate composition.

4. 3. 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 subjected to gas chromatography analysis under the following conditions, the area ratio of a peak appearing in a relative retention time range of 0.64 to 0.72, when the relative retention time of the peak of propylene glycol 1-monomethyl ether 2-acetate is set to 1.00, is 800 ppm or less. (test) The propylene glycol monomethyl ether acetate composition is heated to 80° C. in a nitrogen atmosphere in a borosilicate glass vessel and maintained at that temperature for 5 days. (Gas Chromatography Analysis Conditions) Analytical column: a column with a stationary phase of polyethylene glycol, length 30 m, inner diameter 0.25 mm, and film thickness 0.25 μm Heating conditions: After holding at 50°C for 10 minutes, heat to 250°C at 5°C / min Sample introduction temperature: 250°C Carrier gas: Nitrogen Column gas flow rate: 1.0 mL / min Detector and detection temperature: Hydrogen flame ionization detector, 250°C Control mode: Column flow rate Split ratio: 50:1 Injection volume: 2.0μL

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