Propylene glycol monomethyl ether acetate products

Abstract

A propylene glycol monomethyl ether acetate product contains propylene glycol 1-monomethyl ether 2-acetate, acetic acid, and water, wherein, based on 100% by mass of the propylene glycol monomethyl ether acetate product, the acetic acid content is 5 ppm or more and 50 ppm or less, and based on 100% by mass of the propylene glycol monomethyl ether acetate product, the water content is 20 ppm or more and 250 ppm or less.

Description

Technical Field

[0001] This invention relates to a propylene glycol monomethyl ether acetate product. Background Technology

[0002] Propylene glycol monomethyl ether acetate (hereinafter also referred to as "PMA") is a widely used organic solvent. PMA is produced, for example, by direct esterification of propylene glycol monomethyl ether (hereinafter also referred to as "PM") with acetic acid under specific conditions (see, for example, Patent Document 1).

[0003] Reference List

[0004] Patent Literature

[0005] Patent Document 1: Chinese Unexamined Patent Application Publication No. 1515537 Summary of the Invention

[0006] Technical issues

[0007] It has been shown that when PMA obtained by the method described in Patent Document 1 is stored for a long period of time and its composition is subsequently confirmed, the purity of PMA tends to decrease.

[0008] The present invention was made in view of the above points, and the object of the present invention is to provide a propylene glycol monomethyl ether acetate product with excellent storage stability.

[0009] Problem solved

[0010] The inventors discovered that propylene glycol monomethyl ether acetate products containing specific components can solve the above-mentioned problems, thus completing the present invention.

[0011] That is, the present invention includes the following embodiments. (1)

[0013] A propylene glycol monomethyl ether acetate product comprising:

[0014] Propylene glycol 1-monomethyl ether 2-acetate,

[0015] Acetic acid, and

[0016] Water, of which

[0017] Based on 100% by weight of the propylene glycol monomethyl ether acetate product, the content of acetic acid is 5 ppm or more and 50 ppm or less, and

[0018] The water content, calculated as 100% by weight of the propylene glycol monomethyl ether acetate product, is above 20 ppm and below 250 ppm. (2)

[0020] According to the propylene glycol monomethyl ether acetate product of (1), the ratio of the content of acetic acid to the content of water, expressed as acetic acid content (ppm) / water content (ppm), is 0.01 or more and 1.50 or less. (3)

[0022] According to (1) or (2), when the propylene glycol monomethyl ether acetate product is subjected to the following test 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 set to 1.00, the area of ​​the peak appearing in the relative retention time range of 0.65 to 0.70 is 260 ppm or less:

[0023] (test)

[0024] In a borosilicate glass container, the propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days under a nitrogen atmosphere.

[0025] (Gas Chromatography Analysis Conditions)

[0026] 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.

[0027] Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C.

[0028] Injection temperature: 250℃

[0029] Carrier gas: Nitrogen

[0030] Column gas flow rate: 1.0 mL / min

[0031] Detector and detection temperature: Hydrogen flame ionization detector, 250℃

[0032] Control mode: Column flow

[0033] Flow split ratio: 50:1

[0034] Injection volume: 2.0 μL. (4)

[0036] The propylene glycol monomethyl ether acetate product according to any one of (1) to (3), wherein when the propylene glycol monomethyl ether acetate product is subjected to the following tests and then subjected to gas chromatography analysis under the following conditions, the peak area of ​​ethyl acetate is less than 12 ppm:

[0037] (test)

[0038] In a borosilicate glass container, the propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days under a nitrogen atmosphere.

[0039] (Gas Chromatography Analysis Conditions)

[0040] 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.

[0041] Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C.

[0042] Injection temperature: 250℃

[0043] Carrier gas: Nitrogen

[0044] Column gas flow rate: 1.0 mL / min

[0045] Detector and detection temperature: Hydrogen flame ionization detector, 250℃

[0046] Control mode: Column flow

[0047] Flow split ratio: 50:1

[0048] Injection volume: 2.0 μL. (5)

[0050] According to any one of (1) to (4), the propylene glycol monomethyl ether acetate product, when the propylene glycol monomethyl ether acetate product is subjected to the following test 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 set to 1.00, the area of ​​the peak appearing in the relative retention time range of 0.37 or more and 0.44 or less is 12 ppm or less:

[0051] (test)

[0052] In a borosilicate glass container, the propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days under a nitrogen atmosphere.

[0053] (Gas Chromatography Analysis Conditions)

[0054] 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.

[0055] Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C.

[0056] Injection temperature: 250℃

[0057] Carrier gas: Nitrogen

[0058] Column gas flow rate: 1.0 mL / min

[0059] Detector and detection temperature: Hydrogen flame ionization detector, 250℃

[0060] Control mode: Column flow

[0061] Flow split ratio: 50:1

[0062] Injection volume: 2.0 μL. (6)

[0064] The propylene glycol monomethyl ether acetate product according to any one of (1) to (5), wherein, when the propylene glycol monomethyl ether acetate product is subjected to the following test and then subjected to gas chromatography analysis under the following conditions, the peak area of ​​2-acetoxy-1-propanol is less than 20 ppm:

[0065] (test)

[0066] In a borosilicate glass container, the propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days under a nitrogen atmosphere.

[0067] (Gas Chromatography Analysis Conditions)

[0068] 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.

[0069] Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C.

[0070] Injection temperature: 250℃

[0071] Carrier gas: Nitrogen

[0072] Column gas flow rate: 1.0 mL / min

[0073] Detector and detection temperature: Hydrogen flame ionization detector, 250℃

[0074] Control mode: Column flow

[0075] Flow split ratio: 50:1

[0076] Injection volume: 2.0 μL. (7)

[0078] The propylene glycol monomethyl ether acetate product according to any one of (1) to (6) is used in the manufacture of semiconductors.

[0079] Beneficial effects

[0080] According to the present invention, a propylene glycol monomethyl ether acetate product with excellent storage stability can be provided. Detailed Implementation

[0081] The following will describe in detail the embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). This embodiment is merely an example for illustrating the present invention and is not intended to limit the present invention to the following. The present invention can be implemented with appropriate modifications within its scope.

[0082] Propylene glycol monomethyl ether acetate products

[0083] The propylene glycol monomethyl ether acetate product of this embodiment (hereinafter also referred to as "PMA product") is a propylene glycol monomethyl ether acetate product comprising propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as "PGMEA"), acetic acid, and water. The acetic acid content, calculated as 100% by weight of the propylene glycol monomethyl ether acetate product, is 5 ppm or more and 50 ppm or less, and the water content, calculated as 100% by weight of the propylene glycol monomethyl ether acetate product, is 20 ppm or more and 250 ppm or less (i.e., this PMA product can also be referred to as "PMA composition"). The propylene glycol monomethyl ether acetate product of this embodiment exhibits excellent storage stability.

[0084] The reason for the excellent storage stability of the PMA product of this embodiment is not yet clear. The reasons are speculated as follows, but are not limited thereto.

[0085] During long-term storage, propylene glycol monomethyl ether acetate (PGMEA) products may decompose, generating impurities, which is considered one of the factors affecting storage stability. Examples of causes of decomposition of carboxylic esters such as PGMEA include hydrolysis. Typically, carboxylic esters hydrolyze in the presence of acid and water, becoming carboxylic acids and alcohols. It is believed that carboxylic esters are more prone to hydrolysis at high acid content. However, it is believed that by adjusting the acetic acid and water content in the PMA product of this embodiment to the aforementioned range, transesterification between the alcohol generated from PGMEA hydrolysis and the acetyl groups of PGMEA can be suppressed. As a result, contrary to the aforementioned trend, the hydrolysis of PGMEA is suppressed.

[0086] However, the above points can be seen as a factor that contributes to the excellent storage stability of the PMA product of this embodiment, but the mechanism of action of this embodiment is not limited to this.

[0087] The purpose of using the PMA product in this embodiment is not particularly limited. For example, the PMA product can be used for industrial purposes, such as ink, diluent, pharmaceuticals and pesticides, plasticizers, surfactants, polymer materials, lubricants, adhesives, detergents, electronic materials, and coatings.

[0088] Examples of electronic materials include, but are not limited to, liquid crystal displays (LCDs) and semiconductor devices. The PMA product of this embodiment is preferably used in the manufacture of semiconductor devices due to its excellent storage stability.

[0089] Specific examples of uses related to semiconductor device manufacturing include, but are not limited to, cleaning solutions (e.g., processing solutions used to clean substrate surfaces after resist stripping), pre-wetting solutions (e.g., processing solutions used before resist coating to reduce resist solvent consumption), resist solvents (e.g., processing solutions used to dissolve photosensitive agents or resins), developing solutions (e.g., processing solutions used to remove soluble resins after negative resist exposure), and stripping solutions (e.g., processing solutions used to remove cured resists after etching). From the viewpoint of preventing product defects during semiconductor device manufacturing, the PMA product of this embodiment is preferably used with resist solvents, pre-wetting solutions, solvents for edge rinsing (rinsing to remove resist from the outer periphery of the wafer) and back rinsing (rinsing to remove resist from the back side of the wafer) of negative resist coating, developing solutions for negative resist development, rinsing solutions for rinsing after negative resist development, cleaning solutions or rinsing solutions for removing resist after etching, etc.

[0090] (Propylene glycol 1-monomethyl ether 2-acetate)

[0091] Propylene glycol 1-monomethyl ether 2-acetic acid ester in the PMA product of this embodiment can be identified and quantified by, for example, gas chromatography (hereinafter also referred to as "GC") analysis.

[0092] (Gas Chromatography Analysis)

[0093] 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.

[0094] Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C.

[0095] Injection temperature: 250℃

[0096] Carrier gas: Nitrogen

[0097] Column gas flow rate: 1.0 mL / min

[0098] Detector and detection temperature: Hydrogen flame ionization detector, 250℃

[0099] Control mode: Column flow

[0100] Flow split ratio: 50:1

[0101] Injection volume: 2.0 μL

[0102] The PGMEA content in the PMA product of this embodiment can be appropriately determined according to the intended use of the PMA product of this embodiment, and there are no particular limitations. However, from the perspective of using it for purposes requiring high purity, the peak area ratio relative to the total peak area in the graph obtained from the GC analysis results is preferably 99.95% or more, more preferably 99.96% or more, and even more preferably 99.97% or more. In this embodiment, "total peak area" refers to the sum of the areas of all peaks appearing in the graph obtained from the GC analysis results. For example, when the relative retention time of the PGMEA peak is set to 1.00, "all peaks" in this embodiment can be defined as all peaks that appear when analysis is continued and stopped within a relative retention time of 0.14 to 2.95.

[0103] (acetic acid)

[0104] The PMA product of this embodiment contains acetic acid. From the viewpoint of storage stability, the acetic acid content in the PMA product of this embodiment, based on 100% by mass, is 5 ppm or more and 50 ppm or less, preferably 5 ppm or more and 45 ppm or less, and more preferably 5 ppm or more and 40 ppm or less.

[0105] This content can be determined based on the methods described in the examples described later.

[0106] This content can be adjusted to the above range, for example, by appropriately adding acetic acid after the alkaline treatment described later. This content can also be adjusted to the above range, for example, by appropriately changing the conditions of the alkaline treatment and dehydration treatment (e.g., the treatment time).

[0107] (water)

[0108] The PMA product of this embodiment contains water. From the viewpoint of storage stability, based on 100% by mass of the PMA product of this embodiment, the water content in the PMA product of this embodiment is 20 ppm or more and 250 ppm or less, preferably 23 ppm or more and 230 ppm or less, and more preferably 25 ppm or more and 230 ppm or less.

[0109] The content can be determined based on the methods described in the examples described later.

[0110] The content can be adjusted to the above range, for example, by appropriately adding water after the dehydration treatment described later. The content can also be adjusted to the above range, for example, by appropriately changing the conditions of the dehydration treatment (e.g., the treatment time).

[0111] (The relationship between the content of acetic acid and the content of water)

[0112] From the viewpoint of storage stability, the ratio of acetic acid content to water content in the PMA product of this embodiment, measured as acetic acid content (ppm) relative to 100% by mass of the PMA product of this embodiment / water content (ppm) relative to 100% by mass of the PMA product of this embodiment, is preferably 0.01 or more and 1.50 or less, more preferably 0.02 or more and 1.25 or less, and even more preferably 0.05 or more and 1.10 or less.

[0113] (ingredient A)

[0114] From the viewpoint of storage stability, when the PMA product of this embodiment is subjected to the following tests and then the above-described GC analysis is performed, when 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 relative retention time range of 0.65 or more and 0.70 or less (the substance corresponding to this peak is also referred to as "component A") is preferably 260 ppm or less, more preferably 220 ppm or less, and even more preferably 200 ppm or less.

[0115] (test)

[0116] The propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days in a borosilicate glass container under a nitrogen atmosphere.

[0117] The area ratio can be determined based on the methods described in the embodiments described later.

[0118] The area ratio can be adjusted to the above range, for example, by appropriately adding acetic acid and / or water after the alkaline treatment and / or dehydration treatment described later. The area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the alkaline treatment and / or dehydration treatment (e.g., the treatment time).

[0119] (ethyl acetate)

[0120] From the viewpoint of storage stability, when the PMA product of this embodiment is subjected to the above-described test and then subjected to the above-described GC analysis, the peak area of ​​ethyl acetate is preferably 12 ppm or less, more preferably 10 ppm or less, and even more preferably 9 ppm or less.

[0121] The area ratio can be determined based on the methods described in the embodiments described later.

[0122] The area ratio can be adjusted to the above range, for example, by appropriately adding acetic acid and / or water after the alkaline treatment and / or dehydration treatment described later. The area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the alkaline treatment and / or dehydration treatment (e.g., the treatment time).

[0123] (Ingredient B)

[0124] From the viewpoint of storage stability, when the PMA product of this embodiment is subjected to the above-described test and then subjected to the above-described GC analysis, when 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 relative retention time range of 0.37 or more and 0.44 or less (the substance corresponding to the peak is also referred to as "component B") is preferably 12 ppm or less, more preferably 10 ppm or less, and even more preferably 8 ppm or less.

[0125] The area ratio can be determined based on the methods described in the embodiments described later.

[0126] The area ratio can be adjusted to the above range, for example, by appropriately adding acetic acid and / or water after the alkaline treatment and / or dehydration treatment described later. The area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the alkaline treatment and / or dehydration treatment (e.g., the treatment time).

[0127] (2-Acetoxy-1-propanol)

[0128] From the viewpoint of storage stability, when the PMA product of this embodiment is subjected to the above-described test and then subjected to the above-described GC analysis, the peak area of ​​2-acetoxy-1-propanol is preferably 20 ppm or less, more preferably 18 ppm or less, and even more preferably 16 ppm or less.

[0129] The area ratio can be determined based on the methods described in the embodiments described later.

[0130] The area ratio can be adjusted to the above range, for example, by appropriately adding acetic acid and / or water after the alkaline treatment and / or dehydration treatment described later. The area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the alkaline treatment and / or dehydration treatment (e.g., the treatment time).

[0131] From the viewpoint of storage stability, when the PMA product of this embodiment is subjected to the above-described test and then subjected to the above-described GC analysis, the peak area ratio of PGMEA is preferably 99.93% or more of the total peak area, more preferably 99.94% or more, and even more preferably 99.95% or more.

[0132] The area ratio can be determined based on the methods described in the embodiments described later.

[0133] The area ratio can be adjusted to the above range, for example, by appropriately adding acetic acid and / or water after the alkaline treatment and / or dehydration treatment described later. The area ratio can also be adjusted to the above range, for example, by appropriately changing the conditions of the alkaline treatment and / or dehydration treatment (e.g., the treatment time).

[0134] <Manufacturing Method of Propylene Glycol Monomethyl Ether Acetate Products>

[0135] The manufacturing method of the PMA product in this embodiment is not particularly limited, but the following method (hereinafter also referred to as "manufacturing method A") is preferred. Manufacturing 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): alkali-treating the second product to obtain a third product; step (d): distilling the third product to obtain a fourth product; and step (e): dehydrating the fourth product to obtain the PMA product. The amounts of acetic acid and water in the PMA product can be adjusted by steps (c) and (e), and the method may further include step (f): adding acetic acid and / or water to the product obtained by step (e) to obtain the PMA product.

[0136] (Step (a))

[0137] In step (a), a first product containing PGMEA is obtained. Step (a) may include operations to prepare PGMEA based on conventionally known methods. Examples of methods for preparing PGMEA include, but are not limited to, the method described in Chinese Unexamined Patent Application Publication No. 1515537. Specifically, PGMEA can be prepared by direct esterification of PM with acetic acid. The first product may contain reactants, catalysts, byproducts, etc., that can be used in the reaction to prepare PGMEA.

[0138] (Step (b))

[0139] In step (b), the first product is distilled to obtain the second product. Examples of specific distillation operations include, but are not limited to, atmospheric distillation and vacuum distillation, and such distillations can be repeated. In this step, it is possible to remove reactants, catalysts, byproducts, etc., that may be present in the first product and can be used in the reaction to prepare PGMEA. Distillation conditions are not particularly limited, but, for example, conditions described in Chinese Unexamined Patent Application Publication No. 1515537 can be used. The amount of acetic acid and water contained in the second product, based on 100% by mass, can be greater than 50 ppm and greater than 250 ppm, respectively.

[0140] (Step (c))

[0141] In step (c), the second product is subjected to alkali treatment to obtain the third product. The alkali treatment conditions are preferably those that reduce the amount of acetic acid in the second product, but there are no particular limitations; for example, KYOWAAD manufactured by Kyowa Chemical Industry Co., Ltd. is used. TMThe second product is subjected to alkali treatment at 500°C. At this point, the amount of acetic acid in the third product can be adjusted, for example, by controlling the treatment time.

[0142] (Step (d))

[0143] In step (d), the third product is distilled to obtain a fourth product. Examples of specific distillation operations include, but are not limited to, vacuum distillation, and such distillation can be repeated. In this step, inorganic substances that may be present in the third product can be removed. Distillation conditions are not particularly limited, but, for example, distillation can be performed with reference to the conditions described in Chinese Unexamined Patent Application Publication No. 1515537.

[0144] (Step (e))

[0145] In step (e), the fourth product is dehydrated to obtain the PMA product. The dehydration conditions are preferably those that reduce the amount of water in the fourth product, but there are no particular limitations; for example, dehydration can be performed by nitrogen bubbling. In this case, the amount of water in the PMA product can be adjusted, for example, by controlling the treatment time.

[0146] (Step (f))

[0147] In step (f), the amount of acetic acid and / or water in the PMA product can be adjusted by adding acetic acid and / or water to the product obtained in step (e). There is no particular limitation on the amount of acetic acid and / or water added; for example, it can be determined based on the difference between the desired acetic acid content C1 and water content C2 in the PMA product and the acetic acid content C1' and water content C2' in the product obtained in step (e). These contents can be determined based on the methods described in the examples described later.

[0148] Example

[0149] The following describes this embodiment in more detail based on examples. This embodiment is not limited to these examples.

[0150] (Example 1)

[0151] (Step (a))

[0152] The first product containing PGMEA was synthesized according to the method described in Chinese Unexamined Patent Application Publication No. 1515537. Specifically, the first product containing PGMEA was obtained through a direct esterification reaction of PM with acetic acid.

[0153] (Step (b))

[0154] Subsequently, 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, unreacted raw materials are distilled off first, and then the fraction containing PGMEA is recovered.

[0155] Subsequently, the fraction containing PGMEA obtained by atmospheric distillation was fed into a distillation column for vacuum distillation. Specifically, the vacuum level of the distillation column was set to -0.08 MPa (gauge pressure), the temperature inside the column was controlled to be below 110°C, the reflux ratio was set to 1 to 6, and the top fraction (temperature: 98 to 100°C) was recovered as the second product. As a peak area ratio relative to the total peak area obtained from the GC analysis results, the content of propylene glycol 1-monomethyl ether 2-acetic acid ester in the obtained second product was 99.97%. Based on 100% by mass of the second product, the amounts of acetic acid and water contained in the second product were 90 ppm and 300 ppm, respectively.

[0156] The contents of PGMEA, acetic acid, and water in the second product were confirmed by the following method. Specifically, the contents of PGMEA and acetic acid were determined by GC analysis under the following conditions. The water content was determined using a Karl Fischer moisture analyzer (product name "AQ-2200A", manufactured by Hiranuma Co., Ltd., Karl Fischer coulometric titration method).

[0157] (Gas Chromatography Analysis)

[0158] Analysis equipment: Nexis GC-2030, manufactured by Shimadzu Corporation.

[0159] Analytical column: DB-WAX (a column with polyethylene glycol as the stationary phase, 30m in length × 0.25mm in inner diameter × 0.25μm in film thickness), manufactured by Agilent Technologies.

[0160] Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C.

[0161] Injection temperature: 250℃

[0162] Carrier gas: Nitrogen

[0163] Column gas flow rate: 1.0 mL / min

[0164] Detector and detection temperature: Hydrogen flame ionization detector, 250℃

[0165] Control mode: Column flow

[0166] Flow split ratio: 50:1

[0167] Injection volume: 2.0 μL

[0168] In the above GC analysis, the PGMEA content was calculated as the percentage of the PGMEA peak area relative to the total peak area in the graph obtained from the GC analysis results. The acetic acid content was calculated by GC analysis using the internal standard method (internal standard: biphenyl).

[0169] In the following examples and comparative examples, the contents of acetic acid and water were also confirmed in the same manner as described above.

[0170] (Step (c))

[0171] Add 0.05% by mass of Kyowa Chemical Industry Co., Ltd. to the second product obtained above (100% by mass). TM At 500°C, stir for 60 minutes to remove acetic acid by adsorption. Filter the solution using a PTFE membrane filter manufactured by ADVANTEC (model: T020A047A, pore size: 0.20 μm) to obtain the third product.

[0172] (Step (d))

[0173] Subsequently, the third product was introduced into a distillation column, the vacuum degree inside the distillation column was set to -0.08 MPa (gauge pressure), the temperature inside the distillation column was controlled below 110℃, and the reflux ratio was set to 1 to 6, so that the fraction at the top of the column (98 to 100℃) was obtained as the fourth product.

[0174] (Step (e))

[0175] The fourth product was dehydrated by bubbling nitrogen gas (filtered through a Kinoshita-type spherical filter manufactured by Kinoshita Rika Kogyo Co., Ltd., model: 501G-1, filter diameter: 10 mm, filter pore size: 100 to 120 μm) at a rate of 3 to 5 L / min for 90 minutes to obtain the PMA product of Example 1. The PMA product contained 5 ppm of acetic acid and 55 ppm of water per 100% by mass.

[0176] Subsequently, the PMA product was subjected to the following test: The PMA product was placed in a 110 ml borosilicate glass container, nitrogen gas was introduced into the container, the container was then sealed, and the PMA product was heated using a thermostat (product name "ST-110B1", manufactured by ESPEC) and kept at 80°C for 5 days.

[0177] Gas chromatography analysis was performed on the PMA products after the experiment under the following conditions.

[0178] (Gas Chromatography Analysis Conditions)

[0179] Analysis equipment: Nexis GC-2030 (manufactured by Shimadzu Corporation)

[0180] Analytical column: DB-WAX (manufactured by Agilent Technologies, a column with polyethylene glycol as the stationary phase, 30m in length × 0.25mm in inner diameter × 0.25μm in film thickness)

[0181] Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C.

[0182] Injection temperature: 250℃

[0183] Carrier gas: Nitrogen

[0184] Column gas flow rate: 1.0 mL / min

[0185] Detector and detection temperature: Hydrogen flame ionization detector, 250℃

[0186] Control mode: Column flow

[0187] Flow split ratio: 50:1

[0188] Injection volume: 2.0 μL

[0189] The GC diagram B obtained after the above experiments was compared with the GC diagram A obtained before the experiments. Substances with peak area fractions less than 5 ppm in diagram A and greater than 5 ppm in diagram B were considered to have a significant impact on the storage stability of PMA products, and their amounts were evaluated. Specifically, in GC diagram B, with a relative retention time of 1.00 for propylene glycol 1-monomethyl ether 2-acetate, the area fractions of the peaks at relative retention times of 0.66 and 0.40 were 135 ppm and 7 ppm, respectively. In GC diagram B, the area fractions of ethyl acetate and 2-acetoxy-1-propanol were 8 ppm and 15 ppm, respectively. Details of the analytical results are shown in Table 1.

[0190] (Example 2)

[0191] Except for changing the stirring time in step (c) of Example 1 to 45 minutes and the bubbling time in step (e) of Example 1 to 100 minutes, the PMA product of Example 2 was obtained in the same manner as in Example 1. The PMA product was subjected to the same tests as in Example 1, and then subjected to the same gas chromatographic analysis as in Example 1. Details of the analytical results are shown in Table 1.

[0192] (Example 3)

[0193] Except for changing the stirring time in step (c) of Example 1 to 40 minutes and the bubbling time in step (e) of Example 1 to 30 minutes, the PMA product of Example 3 was obtained in the same manner as in Example 1. The PMA product was subjected to the same tests as in Example 1, and then subjected to the same gas chromatographic analysis as in Example 1. Details of the analytical results are shown in Table 1.

[0194] (Example 4)

[0195] Except for changing the stirring time in step (c) of Example 1 to 25 minutes and the bubbling time in step (e) of Example 1 to 80 minutes, the PMA product of Example 4 was obtained in the same manner as in Example 1. The PMA product was subjected to the same tests as in Example 1, and then subjected to the same gas chromatographic analysis as in Example 1. Details of the analytical results are shown in Table 1.

[0196] (Comparative Example 1)

[0197] Except for changing the stirring time in step (c) of Example 1 to 60 minutes and the bubbling time in step (e) of Example 1 to 120 minutes, the PMA product of Comparative Example 1 was obtained in the same manner as in Example 1. The PMA product was subjected to the same tests as in Example 1, and then subjected to the same gas chromatographic analysis as in Example 1. Details of the analytical results are shown in Table 1.

[0198] (Comparative Example 2)

[0199] Except for changing the stirring time in step (c) of Example 1 to 45 minutes and the bubbling time in step (e) of Example 1 to 120 minutes, the PMA product of Comparative Example 2 was obtained in the same manner as in Example 1. The PMA product was subjected to the same tests as in Example 1, and then subjected to the same gas chromatographic analysis as in Example 1. Details of the analytical results are shown in Table 1.

[0200] (Comparative Example 3)

[0201] Except for changing the stirring time in step (c) of Example 1 to 5 minutes and the bubbling time in step (e) of Example 1 to 110 minutes, the PMA product of Comparative Example 3 was obtained in the same manner as in Example 1. The PMA product was subjected to the same tests as in Example 1, and then subjected to the same gas chromatographic analysis as in Example 1. Details of the analytical results are shown in Table 1.

[0202] [Table 1]

[0203]

Claims

1. A propylene glycol monomethyl ether acetate product, comprising: Propylene glycol-1-monomethyl ether-2-acetate, Acetic acid, and Water, of which Based on 100% by weight of the propylene glycol monomethyl ether acetate product, the content of acetic acid is 5 ppm or more and 50 ppm or less. Based on 100% by weight of the propylene glycol monomethyl ether acetate product, the water content is above 20 ppm and below 250 ppm, and The ratio of the acetic acid content to the water content, expressed as acetic acid content ppm / water content ppm, is 0.01 or more and 1.50 or less.

2. The propylene glycol monomethyl ether acetate product according to claim 1, wherein, When the propylene glycol monomethyl ether acetate product was subjected to the following tests and then subjected to gas chromatography analysis 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 relative retention time range of 0.65 to 0.70 was 260 ppm or less: test In a borosilicate glass container, the propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days under a nitrogen atmosphere. Gas chromatography analysis conditions 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. Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C. Injection 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 Flow split ratio: 50:1 Injection volume: 2.0 μL.

3. The propylene glycol monomethyl ether acetate product according to claim 1 or 2, wherein, When the propylene glycol monomethyl ether acetate product was subjected to the following tests and then subjected to gas chromatography analysis under the following conditions, the peak area of ​​ethyl acetate was less than 12 ppm: test In a borosilicate glass container, the propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days under a nitrogen atmosphere. Gas chromatography analysis conditions 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. Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C. Injection 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 Flow split ratio: 50:1 Injection volume: 2.0 μL.

4. The propylene glycol monomethyl ether acetate product according to claim 1 or 2, wherein, When the propylene glycol monomethyl ether acetate product was subjected to the following tests and then subjected to gas chromatography analysis under the following conditions, with the relative retention time of the peak of propylene glycol-1-monomethyl ether-2-acetate set to 1.00, the peak area in the relative retention time range of 0.37 to 0.44 was less than 12 ppm: test In a borosilicate glass container, the propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days under a nitrogen atmosphere. Gas chromatography analysis conditions 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. Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C. Injection 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 Flow split ratio: 50:1 Injection volume: 2.0 μL.

5. The propylene glycol monomethyl ether acetate product according to claim 1 or 2, wherein, When the propylene glycol monomethyl ether acetate product was subjected to the following tests and then subjected to gas chromatography analysis under the following conditions, the peak area of ​​2-acetoxy-1-propanol was less than 20 ppm: test In a borosilicate glass container, the propylene glycol monomethyl ether acetate product was heated to 80°C and maintained for 5 days under a nitrogen atmosphere. Gas chromatography analysis conditions 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. Heating conditions: Hold at 50°C for 10 minutes, then increase the temperature at a rate of 5°C / minute until reaching 250°C. Injection 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 Flow split ratio: 50:1 Injection volume: 2.0 μL.

6. Use of the propylene glycol monomethyl ether acetate article according to claim 1 or 2 for the manufacture of semiconductors.

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