JP3274127B2 - Handling method of vinylpyrrolidone polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a handling method capable of suppressing a change in physical properties of a vinylpyrrolidone-based polymer.

[0002]

2. Description of the Related Art Vinylpyrrolidone-based polymers such as polyvinylpyrrolidone and vinylpyrrolidone copolymer have advantages and advantages such as biocompatibility, safety and hydrophilicity.
BACKGROUND ART Conventionally, it has been widely used in various fields such as pharmaceuticals, cosmetics, adhesives, paints, dispersants, inks, and electronic components. These vinylpyrrolidone-based polymers are generally often produced by solution polymerization, and are usually obtained in a solution state. Then, the obtained vinylpyrrolidone-based polymer solution is, for example, purified and concentrated if necessary, filled in a container, sealed and stored in a solution state, or
After passing through processes such as drying, crushing, and classification, the powder is filled into a container and sealed.

[0003] However, the vinylpyrrolidone-based polymer may be in the form of powder or solution, regardless of its form.
It is generally known that there is a problem in storage stability. For example, during long-term storage or high-temperature storage, physical properties such as molecular weight (K value) and Hazen color number tend to change over time. Also, when the product form is a powder, for example, a drying step in which the vinylpyrrolidone polymer is exposed to a high temperature,
In the crushing process, etc., which is strongly diffused into the air in the device,
In many cases, physical properties such as molecular weight (K value) and Hazen color number change. Furthermore, when the product of vinylpyrrolidone polymer is used after being dissolved or diluted,
Particularly at high temperatures, physical properties such as molecular weight (K value) and Hazen color number tended to change. As described above, the vinylpyrrolidone-based polymer has a problem that the physical properties such as the molecular weight (K value) and the Hazen color number are apt to change in all situations where the polymer is handled.

[0004]

The problems to be solved by the present invention include, for example, a long-term storage, a high-temperature storage, and a molecular weight (K value) or Hazen in various situations such as a drying step and a pulverizing step. An object of the present invention is to provide a method for handling a vinylpyrrolidone-based polymer that can suppress a change in physical properties such as the number of colors.

[0005]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, they found that the vinylpyrrolidone-based polymer was easily oxidatively degraded under the influence of oxygen, and completed the present invention. That is, the method for handling a vinylpyrrolidone-based polymer according to the present invention is such that the oxygen concentration in the gas phase in contact with the vinylpyrrolidone-based polymer is 50%.
000 ppm or less.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail. The vinylpyrrolidone-based polymer in the present invention is, specifically, a homopolymer of vinylpyrrolidone and / or a copolymer of vinylpyrrolidone and any other polymerizable monomer, for example, solution polymerization. And the like by a conventionally known production method. The optional polymerizable monomer that can be copolymerized with vinylpyrrolidone is not particularly limited, and specifically includes, for example, 1) methyl (meth) acrylate,
(Meth) acrylates such as ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate; 2) (meth) acrylamide and N-monomethyl (Meth) acrylamide derivatives such as (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide; 3)
Dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine,
Basic unsaturated monomers such as vinylimidazole and salts or quaternary compounds thereof; 4) vinylamides such as vinylformamide, vinylacetamide and vinyloxazolidone; 5) (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid Carboxyl group-containing unsaturated monomers such as acids and salts thereof; 6) unsaturated anhydrides such as maleic anhydride and itaconic anhydride; 7) vinyl esters such as vinyl acetate and vinyl propionate; Carbonate and its derivatives; 9) styrene and its derivatives; 1
0) Ethyl (meth) acrylate-2-sulfonate and its derivatives; 11) Vinyl sulfonic acid and its derivatives; 12) Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether;
3) olefins such as ethylene, propylene, octene and butadiene; and the like. Among them, 1) to 8) are particularly preferable from the viewpoint of copolymerizability with vinylpyrrolidone. These may be used alone, or two or more may be mixed and copolymerized with vinylpyrrolidone.

[0007] The proportion of vinylpyrrolidone in the vinylpyrrolidone copolymer is not particularly limited, but is preferably at least 0.1 mol%, more preferably at least 5 mol%, more preferably at least 20 mol%, based on all monomer components. Most preferred. When vinylpyrrolidone in the copolymer is less than 0.1 mol%, deterioration of the polymer, which is a subject of the present invention, is hardly recognized. In the present invention, the oxygen concentration in the gas phase in contact with the vinylpyrrolidone polymer is 50,000 ppm
It is important to: The oxygen concentration is preferably 10,000 ppm or less, more preferably 1000 pp.
m, and the lower the oxygen concentration,
The stability at the time of handling the vinylpyrrolidone-based polymer can be more effectively improved. The oxygen concentration is 5000
If it exceeds 0 ppm, physical properties such as molecular weight (K value) will significantly change during long-term storage, high-temperature storage, and in the drying step and the pulverizing step.

Here, the gaseous phase is a portion other than the solid phase and / or liquid phase occupied by the vinylpyrrolidone-based polymer, and the oxygen concentration in the gaseous phase means the oxygen content in a unit volume of the gaseous phase. Means the absolute amount of For example, when a vinylpyrrolidone-based polymer is accommodated in a closed container, the oxygen concentration in the gas phase is the ratio of the volume of oxygen in the gas phase in the container at normal pressure to the volume of the gas phase. The oxygen concentration is
For example, it can be easily measured with a commercially available oxygen concentration meter such as a galvanic cell diffusion type or a zirconia sensor type. In the present invention, as a first means for reducing the oxygen concentration in the gas phase in contact with the vinylpyrrolidone-based polymer, the space in which the vinylpyrrolidone-based polymer is present is sealed, and the inside of the sealed space is evacuated. It is preferable to keep the state. For example, during storage, the vinylpyrrolidone-based polymer may be housed in a closed container, and the inside of the container may be kept in a vacuum state. What is necessary is just to put a device in the closed space made, and to grind it.

The specific method of vacuuming is not particularly limited, and the pressure in the closed space may be reduced by a usual method. The degree of vacuum is not particularly limited, but it is preferable that the vacuum is applied so that the container or the like is not damaged. In the present invention, as the second means for reducing the oxygen concentration in the gaseous phase in contact with the vinylpyrrolidone-based polymer, for example, the gaseous phase in contact with the vinylpyrrolidone-based polymer is converted into an inert gas and / or carbon dioxide. The method of replacing with a gas is preferable. More preferably, the space in which the vinylpyrrolidone polymer is present is sealed, and the sealed space is completely replaced with an inert gas and / or carbon dioxide gas. Also,
In particular, when preserving the vinylpyrrolidone-based polymer, when carbon dioxide gas is used as a replacement gas, the change in the physical properties of the vinylpyrrolidone-based polymer is suppressed, and the unreacted vinyl remaining in the vinylpyrrolidone-based polymer is suppressed. Pyrrolidone is more preferred because it can be reduced by hydrolysis during storage.

[0010] The inert gas is a gas having poor reactivity, and specific examples thereof include gases such as helium, neon, and argon of Group 0 of the periodic table; nitrogen gas; and the like. Among them, nitrogen gas is preferable because it is easily available at low cost. The specific method of replacing with an inert gas and / or a carbon dioxide gas is not particularly limited, but when replacing with a gas, for example, a volume of at least 5 times or more the volume in a closed space is used. Preferably, a gas is introduced. It is preferable that the gas is sealed after the inside of the sealed space is once decompressed to a vacuum and the air is expelled, so that the gas can be replaced more efficiently. Further, when the vinylpyrrolidone-based polymer is a solution, it is preferable to bubble the solution with a gas inlet tube or the like in order to remove oxygen dissolved in the solution.

In the present invention, as a third means for reducing the oxygen concentration in the gas phase in contact with the vinylpyrrolidone polymer, for example, a space in which the vinylpyrrolidone polymer is present is sealed, It is preferable to enclose an oxygen scavenger in the closed space. As the oxygen absorber,
There is no particular limitation as long as oxygen can be removed by a chemical reaction.However, from the viewpoint of safety and ease of use, for example, iron powder, iron oxide, iron hydroxide, or a mixture thereof is gas-permeable. What is enclosed with a conductive film is preferable. Specifically, if a commercially available oxygen absorber such as "Ageless" manufactured by Mitsubishi Gas Chemical Co., Ltd., "Vitalon" manufactured by Toa Gosei Chemical Co., Ltd., or "Moduran" manufactured by Nippon Kayaku Co., Ltd. is used. Good.

In each of the above-mentioned means for reducing the oxygen concentration, the method for sealing the space in which the vinylpyrrolidone polymer is present is not particularly limited. What is necessary is just to accommodate a vinylpyrrolidone type polymer in a container. The sealable container is not particularly limited in its material and shape, but is preferably a highly airtight container so that gas absorption and outflow hardly occur. Specifically, examples of the material include glass, metal, various plastics, and the like.
Examples of the shape include a bottle, a can, and a bag. In the present invention, one of the first, second and third means described above as a method for reducing the oxygen concentration in the gas phase in contact with the vinylpyrrolidone polymer is preferably used in combination with one method, preferably a plurality of methods. Thereby, the oxygen concentration can be effectively reduced.

[0013] The product form of the vinylpyrrolidone polymer in the present invention is not particularly limited.
It may be in any form such as lump, fibrous, powdery, solution, and film. The produced vinylpyrrolidone-based polymer is, for example, purified in the case of a solution form,
It is commercialized and stored through processes such as concentration and packaging. In the case of a powdery product form, it is made into a product through processes such as drying, pulverization (including coarse crushing and crushing), classification, and packaging, and stored. The handling method of the present invention is applied in all steps from production to production and storage, for example, a reaction device immediately after production, a powdering device, a drying device, and a storage tank. , Transfer line,
In addition, it is important that the oxygen concentration in the gas phase in any working environment in which the polymer is handled is set to a certain concentration or less. Further, the handling method of the present invention, when using a polymerized product, for example, dissolving a powdery product in a solvent, diluting a solution-like product, The present invention is also applicable to the case where a solution obtained by dissolving in a solution or a product in the form of a solution is dried by film formation. In addition, for example, after dissolving, diluting, film-forming and drying the commercialized polymer, and then storing the obtained solution or dried product, it is effective to apply the handling method of the present invention. is there.

In particular, changes in physical properties of the vinylpyrrolidone-based polymer are generally caused by a drying step in which the polymer is exposed to high temperatures during storage (particularly during long-term storage or high-temperature storage), or a strong diffusion into air in an apparatus. The handling method of the present invention is effective to be applied in these situations, since it is remarkably easy to appear in the pulverizing step. When the handling method of the present invention is applied during storage, for example, the first, second, and third means described above as a method for reducing the oxygen concentration in the gas phase in contact with a vinylpyrrolidone-based polymer. Of these, it is preferable to use a plurality of methods in combination, but it is not limited thereto. Specifically, the polymer may be stored in a sealable container, the inside of the container may be evacuated, the gas may be replaced, and a deoxidizer may be sealed.

When the handling method of the present invention is applied to drying, for example, the first, second, and third methods described above as a method for reducing the oxygen concentration in the gas phase in contact with the vinylpyrrolidone-based polymer. Of the above-mentioned means, a method of making the first vacuum and / or a method of replacing with the second gas are preferable, but not limited thereto. In particular,
For example, the pressure in a commonly used drying apparatus such as a belt dryer, a spray dryer, a drum dryer, a compact disk dryer, a fluidized-granulation spray dryer, a fluidized bed dryer, a band dryer, a ribbon dryer, or the like is reduced or a fixed amount is used. Drying may be performed while introducing the above gas.

When the handling method of the present invention is applied to pulverization, for example, the first, second, and third methods described above as a method for reducing the oxygen concentration in the gas phase in contact with a vinylpyrrolidone-based polymer are used. Of these means, a method of replacing with a second gas is preferable, but not limited thereto. Specifically, for example, hammer mill, feather mill,
Ball mill, mortar mill and other commonly used crushing equipment,
The operation may be performed in a gas-replaced atmosphere, preferably in a gas-replaced closed container. In the present invention, the stability of the vinylpyrrolidone polymer during storage is
For example, it can be determined from the rate of decrease in the K value before and after the compulsory test measured by the following method. That is, the vinylpyrrolidone-based polymer sealed and stored in the container was subjected to a forced test in which the entire container was heated and maintained at 120 ° C. for 2 hours. It is dissolved in an arbitrary solvent to be dissolved at a concentration of 10% by weight or less, the viscosity of the solution is measured at 25 ° C. by a capillary viscometer, and the K value indicated by the Fikentcher equation is determined using these measured values. The storage stability of the vinylpyrrolidone-based polymer can be easily determined by looking at the rate of decrease in the K value after the test relative to the initial K value before the forced test. If the rate of decrease is within 5%, stable storage can be achieved without any change in physical properties even during high-temperature storage or long-term storage.

The K value is a value calculated from the following equation using the measured viscosity. (Logηrel) / C = [(75 Ko ² ) / (1+
1.5 Ko C)] + Ko K = 1000 Ko Here, C indicates the number of grams in 100 ml of the solution, and ηre
l indicates the viscosity of the solution with respect to the solvent. In the present invention, the stability of the vinylpyrrolidone-based polymer at the time of drying, pulverization, or the like can be determined by the change in the K value.

In the present invention, the stability of the vinylpyrrolidone-based polymer can also be determined by the Hazen color number measured according to JIS-K-0071-1. In particular, during drying, the coloring usually tends to be noticeable, so it is useful to make a determination based on the number of Hazen colors. As an indication of the molecular weight of the vinylpyrrolidone-based polymer to which the present invention can be applied, the initial value of the K value is not particularly limited, but is preferably applied to a vinylpyrrolidone-based polymer having a K value in the range of 15 to 150. . In addition, since the stability of a vinylpyrrolidone polymer having a high K value is particularly poor, it is more preferable to apply to a vinylpyrrolidone polymer having a K value in the range of 60 to 150.

The vinylpyrrolidone-based polymer treated by the method of the present invention is a compound of a vinylpyrrolidone-based polymer used in various fields such as pharmaceuticals, cosmetics, adhesives, paints, dispersants, inks, and electronic parts. It can be suitably used for the composition.

[0020]

EXAMPLES Hereinafter, examples and comparative examples according to the present invention will be described with respect to storage, drying, pulverization, dissolution and dissolution of products.
The present invention is not limited by the examples, which will be described separately for each dilution. The K value of each of Examples and Comparative Examples was determined by the viscosity measurement method described above, that is, 0.1% of each of the vinylpyrrolidone polymers of Examples and Comparative Examples.
The viscosity measured by a method of measuring the relative viscosity with a capillary viscometer at 25 ° C. using a ２2% aqueous solution was calculated by applying the formula of the Fikentcher. The Hazen color numbers of the examples and comparative examples were measured according to JIS-K-0071-1. That is, Hazen standard colorimetric liquids were prepared, and measured by visual comparison with these. In addition, all the measurements were performed with a 5% aqueous solution.

<Example of Storage> [Example 1-1] 100 g of powdery polyvinylpyrrolidone having a K value of 91 was placed in a container with an oxygen sensor having a content of 50 g.
0 ml was placed in a glass container with a sealable lid, and the glass container was set in a glove box. Then, a nitrogen gas was introduced into the glove box for about 30 minutes to adjust the oxygen concentration in the glove box to 20 ppm, and then the container was sealed, and polyvinylpyrrolidone powder was sealed with the nitrogen gas.

This polyvinylpyrrolidone is added to each container in an amount of 1
After heating in an oven at 20 ° C. for 2 hours, it was cooled to room temperature. The K value of the polyvinylpyrrolidone after the heat treatment was 91, and it was confirmed that the K value was not changed. [Example 1-2] 300 g of a 20% aqueous solution of polyvinylpyrrolidone having a K value of 91 was placed in a 500 ml-capacity glass container equipped with an oxygen sensor and having a sealable lid, and the glass container was placed in a glove box. Set inside. Then, nitrogen gas is introduced into the glove box for about 30 minutes, and the oxygen concentration in the glove box is reduced to 20 pp.
m, and at the same time, the solution in the container is supplied at a flow rate of 100 ml / min.
After bubbling for minutes, the container was sealed and an aqueous solution of polyvinylpyrrolidone was sealed with nitrogen gas.

The polyvinylpyrrolidone was prepared according to Example 1
When the same heat treatment as in Example 1 was performed, the K value of the polyvinylpyrrolidone after the heat treatment was 91, and it was confirmed that the K value was not changed. [Example 1-3] A 20% aqueous solution of polyvinylpyrrolidone having a K value of 87 (containing 50 ppm of vinylpyrrolidone)
300 g was placed in a 500 ml-capacity glass container equipped with an oxygen sensor and having a sealable lid, and the glass container was set in a glove box. Then, a carbon dioxide gas is introduced into the glove box for about 30 minutes to bring the oxygen concentration in the glove box to 20 ppm, and at the same time, the solution in the container is flowed at a flow rate of 50 ml / min. After bubbling for 30 minutes, the mixture was sealed, and an aqueous solution of polyvinylpyrrolidone was sealed with carbon dioxide gas. The pH of the solution after bubbling carbon dioxide gas
Was 3.9.

The polyvinylpyrrolidone was prepared according to Example 1
When the same heat treatment as in Example 1 was performed, the K value of the polyvinylpyrrolidone after the heat treatment was 86, and it was confirmed that there was almost no change (decrease rate: 1.1%). Further, this polyvinylpyrrolidone was charged with carbon dioxide gas for 25 minutes.
After storage at 1 ° C. for one month, sampling was performed in a glove box, and vinylpyrrolidone in the solution was quantified by liquid chromatography. As a result, it was confirmed that the concentration was reduced to 1 ppm or less. [Example 1-4] 20 g of powdery polyvinylpyrrolidone having a K value of 89 was placed in a heat-sealable PET bag, and a glass tube equipped with a gas filter at the tip and an oxygen sensor were introduced into the bag. The other part of the bag was sealed by heat sealing. Then, the glass tube is
connected to a vacuum system of
After 5 minutes, remove the glass tube from the vacuum system, seal it quickly,
Polyvinylpyrrolidone powder was sealed in a vacuum. At this time, the oxygen concentration in the bag was 180 ppm.

When the polyvinylpyrrolidone was subjected to the same heat treatment as in Example 1-1 for each bag, the K value of the polyvinylpyrrolidone after the heat treatment was 88, and it was confirmed that there was almost no change (decrease). Rate 1.1%). [Example 1-5] 20 g of powdery polyvinylpyrrolidone having a K value of 91 was added to a container with an oxygen sensor having an inner volume of 100 g.
ml of glass container with a sealable lid. Then, on the back side of the lid, "Ageless S" manufactured by Mitsubishi Gas Chemical Co., Ltd.
A "was fixed, and the lid was closed to form a sealed state and left for 24 hours. The oxygen concentration in the container after standing was 700 ppm.

When this polyvinylpyrrolidone was subjected to the same heat treatment as in Example 1-1 for each container, the K value of the polyvinylpyrrolidone after the heat treatment was 89, and it was confirmed that there was almost no change (decrease). Rate 2.2%). [Example 1-6] Except that the polyvinylpyrrolidone in the powder was replaced with a vinylpyrrolidone / vinyl acetate copolymer (copolymer weight ratio 80/20) having a K value of 70,
In the same manner as in Example 1-1, polyvinylpyrrolidone powder was sealed with nitrogen gas. When this polyvinylpyrrolidone was subjected to the same heat treatment as in Example 1-1 for each container, the K value of the polyvinylpyrrolidone after the heat treatment was 7
It was 0 and it was confirmed that there was no change.

[Comparative Example 1-1] As in Example 1-1,
A glass container containing powdered polyvinylpyrrolidone having a K value of 91 was set in a glove box, and the container was sealed without introducing nitrogen gas into the glove box. At this time, the oxygen concentration in the glove box is 20.
95%. When the same heat treatment as in Example 1-1 was performed on this polyvinylpyrrolidone, the K value of the polyvinylpyrrolidone after the heat treatment was reduced to 84 (decrease rate: 7.7%).

[Comparative Example 1-2] As in Example 1-1,
A glass container containing powdered polyvinylpyrrolidone having a K value of 91 was set in a glove box. Then, a mixed gas of nitrogen gas and air is introduced into the glove box for about 30 minutes to bring the oxygen concentration in the glove box to 8%, and then sealed, and polyvinylpyrrolidone powder is sealed with the mixed gas. did. This polyvinylpyrrolidone was subjected to the same heat treatment as in Example 1-1.
The K value of the polyvinylpyrrolidone after the heat treatment was reduced to 85 (a reduction rate of 6.6%).

[Comparative Example 1-3] As in Example 1-2,
A glass container containing a 20% aqueous solution of polyvinylpyrrolidone having a K value of 91 was set in a glove box, and sealed without introducing nitrogen gas into the glove box. At this time, the oxygen concentration in the glove box was 20.95%. When the same heat treatment as in Example 1-2 was performed on this polyvinylpyrrolidone, the K value of the polyvinylpyrrolidone after the heat treatment was reduced to 85 (decrease rate: 6.6%). <Example of drying> [Example 2-1] A digital hot plate, a nitrogen introducing device and an oxygen sensor whose temperature was set to 150 ° C were set in a glove box, and the oxygen concentration in the glove box became 5000 ppm or less. Nitrogen was introduced as described above. Next, the K value is 88.6 and the Hazen color number is 5
0, 5.2 g of an aqueous solution of polyvinylpyrrolidone having a concentration of 20% by weight was previously prepared on a steel plate having a Teflon (registered trademark) sheet adhered to its surface.
And coated with a spatula so that the film thickness would be uniform. After the surface temperature on the hot plate reached equilibrium, the steel plate coated with the aqueous solution of polyvinylpyrrolidone was quickly placed on the hot plate and dried for 30 minutes.

The K value of the obtained dried product is 88.7,
No change was noted. The Hazen color number was 50, and no coloring was observed. [Example 2-2] The temperature of the digital hot plate was set to 16
Drying was performed in the same manner as in Example 2-1 except that the temperature was set to 0 ° C. The K value of the obtained dried product was 88.5, and almost no change was observed (decrease rate: 0.11%). The Hazen color number was 60, and almost no coloring was observed.

[Example 2-3] Example 2-1 except that the temperature of the digital hot plate was set to 170 ° C.
Drying was performed in the same manner as described above. The K value of the obtained dried product is 88.
1 and little change was observed (decrease rate 0.5
6%). The Hazen color number was 70, and almost no coloring was observed. [Example 2-4] The temperature of the digital hot plate was set to 18
Drying was performed in the same manner as in Example 2-1 except that the temperature was set to 0 ° C.

The K value of the obtained dried product was 88.0,
Little change was observed (decrease rate 0.68%). The Hazen color number was 70, and almost no coloring was observed. [Comparative Example 2-1] Example 2 was repeated except that the same amount of air was introduced instead of introducing nitrogen into the glove box.
Drying was performed in the same manner as -1. At this time, the oxygen concentration in the glove box was 20.95%. The K value of the obtained dried product was 87.7, and a decrease in the K value due to drying was observed (decrease rate: 1.01%). The number of Hazen colors was 60, and the degree of coloring was lower than that of Example 2-1.

Comparative Example 2-2 Comparative Example 2-1 except that the temperature of the digital hot plate was set at 160 ° C.
Drying was performed in the same manner as described above. The K value of the obtained dried product was 87.
7, indicating a decrease in the K value due to drying (decrease rate: 1.01%). The number of Hazen colors was 70, and the degree of coloring was worse than that of Example 2-2. [Comparative Example 2-3] The temperature of the digital hot plate was set to 17
Drying was performed in the same manner as in Comparative Example 2-1 except that the temperature was set to 0 ° C.

The K value of the obtained dried product is 87.5,
The K value was decreased by drying (decrease rate 1.24).
%). Further, the number of Hazen colors is 80, and
The degree of coloration was worse than that of. [Comparative Example 2-4] Setting the temperature of the digital hot plate to 18
Drying was performed in the same manner as in Comparative Example 2-1 except that the temperature was set to 0 ° C. The K value of the obtained dried product was 86.7, and a remarkable decrease in the K value due to drying was observed (decrease rate 2.1).
4%). The number of Hazen colors is 100, and
The degree of coloring was worse than that of No.-4.

<Example of Pulverization> [Example 3-1] A hammer mill equipped with a nitrogen introducing device and an oxygen sensor in a powder collecting part was set in a glove box, and the oxygen concentration in the glove box was 500.
Nitrogen was introduced so as to be 0 ppm or less. Next, the dried polyvinylpyrrolidone having a K value of 89.6 was charged into a hammer mill and pulverized. The K value of the obtained pulverized product was 89.6, and no change was observed. [Comparative Example 3-1] Pulverization was performed in the same manner as in Example 3-1 except that nitrogen was not introduced into the glove box. At this time, the oxygen concentration in the glove box is 20.95%
Met. The K value of the obtained pulverized product was 89.0, and the K value was reduced by pulverization as compared with Example 3-1 (reduction rate: 0.67%). <Example of dissolution / dilution> [Example 4-1] A nitrogen introducing device and an oxygen sensor were set in a glove box, and nitrogen was introduced so that the oxygen concentration in the glove box became 5000 ppm or less. . Next, in the glove box, the K value is 8
9.5 powder of polyvinylpyrrolidone and 10 g of water
90 g was placed in a 300 ml four-necked flask, and the flask was opened at 80 ° C. for 2 hours while the flask was opened.
% Aqueous solution was prepared. The K value of the obtained aqueous solution was 89.4.
And almost no change was observed (decrease rate 0.11).
%).

[Embodiment 4-2] 2 where K value is 89.5
50 g of a 0% aqueous solution of polyvinylpyrrolidone and 150 g of water
5-5 in the same manner as in Example 4-1 except that
% Aqueous solution was prepared. The K value of the obtained aqueous solution was 89.5.
And no change was observed. [Comparative Example 4-1] A 5% aqueous solution was prepared in the same manner as in Example 4-1 except that the reaction was not performed in the glove box. At this time, the oxygen concentration in the working environment was 20.95%. The K value of the obtained aqueous solution was 86.7, and a decrease in the K value was observed as compared with Example 4-1 (decrease rate 3.1).
3%).

[Comparative Example 4-2] A 5% aqueous solution was prepared in the same manner as in Example 4-2 except that the reaction was not performed in the glove box. At this time, the oxygen concentration in the working environment is 2
0.95%. The K value of the obtained aqueous solution was 86.9.
And a decrease in the K value was observed as compared with Example 4-2 (a decrease rate of 2.91%).

[0038]

According to the method for handling a vinylpyrrolidone-based polymer of the present invention, the molecular weight (K value) and the Hazen color can be obtained in all situations such as long-term storage, high-temperature storage, drying and pulverization. Changes in physical properties such as numbers can be suppressed. In addition, at the time of storage, if the inside of the container containing the vinylpyrrolidone polymer is replaced with carbon dioxide gas,
Further, vinylpyrrolidone having a carcinogenic property which easily remains as a monomer in the vinylpyrrolidone-based polymer can be reduced by hydrolysis during storage.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akio Naka 5-8, Nishimitabi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Hideyuki Nishibayashi 5-8, Nishimitabi-cho, Suita-shi, Osaka (56) References JP-A-11-199603 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 3/00 C08F 6/00 C08L 39/06

Claims (5)

(57) [Claims] 1. A method for handling a vinylpyrrolidone polymer, wherein the oxygen concentration in the gas phase in contact with the vinylpyrrolidone polymer is 50,000 ppm or less. 2. A closed space in which a vinylpyrrolidone polymer is present, and the inside of the closed space is kept in a vacuum state.
A method for handling the vinylpyrrolidone-based polymer according to claim 1. 3. The method for handling a vinylpyrrolidone-based polymer according to claim 1, wherein the gas phase in contact with the vinylpyrrolidone-based polymer is replaced with an inert gas and / or a carbon dioxide gas. 4. The method for handling a vinylpyrrolidone polymer according to claim 3, wherein the space in which the vinylpyrrolidone polymer is present is sealed. 5. The vinylpyrrolidone polymer according to claim 1, wherein a space in which the vinylpyrrolidone polymer is present is sealed, and an oxygen scavenger is enclosed in the sealed space. How to handle coalescence.