JP2001206435A - Agricultural chemical packaging film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural chemical packaging film which is excellent in solubility in water, resistance to chemicals and biodegradability. SOLUTION: The agricultural chemical packaging film comprises a polyvinyl alcohol based resin wherein 1,2-glycol bonding amount is 1.8 mol% or more and a saponification value is 92 to 99.9 mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film made of a specific polyvinyl alcohol-based resin,
The present invention relates to an agrochemical packaging film having excellent chemical resistance and biodegradability, and particularly useful for agrochemical unit packaging.

[0002]

2. Description of the Related Art In recent years, various chemicals such as agricultural chemicals are sealedly packaged (unit wrapped) in a unit amount in a water-soluble film, and are put into water in the form of the package when used.
A method of dissolving or dispersing the contents together with the packaging film in water has been widely used. The advantages of this unit package are that it can be used without directly touching dangerous chemicals during use, that it is not necessary to weigh it at the time of use because a fixed amount is packed, and that post-treatment such as packaging containers and bags is unnecessary or simple And so on.

Conventionally, as such a water-soluble film for unit packaging, an unmodified partially saponified polyvinyl alcohol (hereinafter, "polyvinyl alcohol" is sometimes referred to as "PVA") film has been used. These water-soluble films are easily soluble in cold water and have excellent mechanical strength and good performance, but are used in formulating pesticides and pesticides (activators, dispersants, etc.). Agents, carriers, etc.) gradually react with the PVA-based film, and the water solubility and impact strength of the film decrease over time. When stored for a long period of time, the film becomes insoluble or hardly soluble in water, Often leaks occur and can no longer be used,
Had been a problem. In addition, from the viewpoints of workability, process passability, environmental problems, and the like, it is required that the film has stiffness and has many performances such as excellent biodegradability.
However, this unmodified partially saponified PVA has a problem that the film is not sufficiently stiff or biodegradable. Due to these film properties, unit packaging of dangerous pesticides has not been widely put into practical use despite the great advantages.

As one of measures against such a problem,
Attempts have been made to use films made of carboxylic acid-modified PVA or sulfonic acid-modified PVA. However, the film may not have sufficient heat resistance, or the water-soluble property may deteriorate with time depending on the modified species.
In addition, the biodegradability is greatly reduced by these denaturations, which may lead to environmental problems.

Further, in addition to acid modification, attempts have been made to use a film made of PVA into which an oxyalkylene group, a cationic group, or the like has been introduced. When formed into a film, the film strength is extremely reduced, or becomes hard and brittle in winter with low humidity due to increased humidity dependency,
On a rainy day, the film can be quite loose.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide features such as water solubility, process passability, and biodegradability that cannot be simultaneously satisfied with a conventional water-soluble film made of a PVA-based polymer. Another object of the present invention is to provide an improved agricultural chemical packaging film.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, the 1,2-glycol bond amount is at least 1.8 mol% and the degree of saponification is from 92 to 99.9.
The present inventors have found that a film composed of a mole% of a PVA-based resin achieves the above object and is very useful as a film for packaging agricultural chemicals, thereby completing the present invention.

That is, in the present invention, the 1,2-glycol bond amount is 1.8 mol% or more, and the saponification degree is 92 to 99.9.
The present invention relates to a film for packaging agrochemicals, comprising a mol% of polyvinyl alcohol resin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The PVA-based resin used in the present invention is a saponified product of a vinyl ester polymer or a copolymer of a vinyl ester and another vinyl monomer. Here, examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl benzoate, vinyl stearate, vinyl pivalate, vinyl versatate, and the like. However, vinyl acetate is preferred from the viewpoint of industrial productivity and the easiness of forming a 1,2-glycol bond.

Examples of vinyl monomers copolymerizable with vinyl esters include α-olefins. Among them, ethylene, propylene, n
Α-olefins having 4 or less carbon atoms, such as butene and isobutylene, are preferred, and ethylene is particularly preferred in that the biodegradability of the resulting film is improved. Α in PVA-based resin
-The olefin unit content is preferably 0.1 to 10 mol%. Other copolymerizable vinyl monomers include acrylic acid and its salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, acrylic T-butyl acid, acrylic acid 2-
Acrylates such as ethylhexyl, dodecyl acrylate and octadecyl acrylate; methacrylic acid and its salts; methyl methacrylate, ethyl methacrylate;
Methacrylates such as n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate; Acrylamide;
Acrylamide derivatives such as N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its salts, N-methylolacrylamide and its derivatives; methacryl Amide; N-
Methacrylamide derivatives such as methyl methacrylamide, N-ethyl methacrylamide, methacrylamidopropanesulfonic acid and salts thereof, methacrylamidopropyldimethylamine and salts thereof, N-methylol methacrylamide and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n- Vinyl ethers such as propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride, and fluorine. Vinyl halides such as vinyl halide and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; Or an ester thereof; vinyl silyl compounds such as vinyltrimethoxysilane; N- vinylpyrrolidone; N- vinylformamide, N- vinyl amides such as N- vinylacetamide; is isopropenyl acetate and the like. From the viewpoint of biodegradability, the content of these vinyl monomers is usually 5 mol% or less.

As the method for producing the vinyl ester (co) polymer, conventionally known polymerization methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method and an emulsion polymerization method can be applied. As the polymerization catalyst, an azo-based catalyst, a peroxide-based catalyst, a redox-based catalyst, or the like is appropriately used depending on the polymerization method.

For the saponification reaction of the vinyl ester (co) polymer, alcoholysis and hydrolysis with a conventionally known alkali catalyst or acid catalyst can be applied. Among these, a saponification reaction using a sodium hydroxide catalyst using methanol as a solvent is simple and most preferable.

The degree of saponification of the PVA resin used in the present invention is 92 to 99.9 mol%, preferably 95 to 9 mol%.
9 mol%. PVA having a degree of saponification in the above range
By using a system resin, a film having excellent chemical resistance, high strength, and stiffness can be obtained. When the degree of saponification of PVA is less than 92 mol%, when packaging the pesticide with the obtained film, the water solubility of the film decreases over time, the mechanical strength deteriorates, or A film with waist cannot be obtained. Conversely, 99.9 mol%
When the ratio exceeds the above range, the water solubility of the obtained film is lowered, and a problem in film production occurs.

The degree of polymerization of the PVA resin used in the present invention is preferably 500 or more, more preferably 700 or more, from the viewpoints of mechanical strength, toughness, impact resistance, chemical resistance and the like of the obtained film. Is more preferable, and more preferably 900 or more. From the viewpoint of industrial productivity, the degree of polymerization of the PVA-based resin is preferably 3000 or less. Further, from the viewpoint of impact resistance required when the obtained film is used as a bag, the degree of polymerization of the PVA-based polymer is preferably from 1,000 to 3,000.

[0015] The PVA resin used in the present invention, 1,2
-The amount of glycol bond is at least 1.8 mol%, preferably at least 2.2 mol%, more preferably at least 2. mol%.
5 mol% or more. The 1,2-glycol bond amount can be controlled by various methods such as the type of vinyl ester, the type of polymerization solvent, the polymerization temperature, and the copolymerization of vinylene carbonate. Among these, the method of controlling with the polymerization temperature is simple and preferable. For example, the polymerization is preferably performed at 80 to 200 ° C, more preferably at 90 to 180 ° C, and even more preferably at 100 to 180 ° C. The upper limit of the 1,2-glycol bond amount is not particularly limited, but when the polymerization temperature is increased to increase the 1,2-glycol bond amount, or when vinylene carbonate or the like is copolymerized, the degree of polymerization decreases. There is a
The amount of glycol bond is preferably 3.5 mol% or less, more preferably 3.2 mol% or less, and 3.0 mol% or less.
More preferably, it is at most mol%.

The PVA resin used in the present invention preferably has a short chain branching amount of 0.03 mol% or more, and more preferably has a short chain branching amount of 0.05 mol% or more. Short-chain branching can be controlled by various methods such as the type of vinyl ester, the type of polymerization solvent, and the polymerization temperature. Among these, the method of controlling with the polymerization temperature is simple and preferable. As the content of short-chain branches increases, the crystallinity of the PVA-based resin decreases, and a preferable film can be obtained without decreasing the water solubility even at a high degree of saponification. In addition, the content of the short-chain branch described in this specification is a short chain (side chain) composed of 1 to 5 vinyl alcohol units branched from the main chain of polyvinyl alcohol. The content of the short-chain branch refers to the ratio (mol%) of the vinyl alcohol unit constituting the short chain to the total vinyl alcohol unit, and specifically,
It can be measured according to the analysis method described in the section of Examples.

The method for producing the film of the present invention using the above-mentioned PVA-based resin is not particularly limited and is appropriately selected depending on the required film thickness and intended purpose.
Cast film forming method from VA solution, dry film forming method (extrusion into inert gas such as air or nitrogen), wet film forming method (PV
Extrusion of A-type resin into poor solvent), dry-wet film formation method, gel film formation method and the like. Examples of the solvent used for preparing the PVA solution include dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethylene glycol, glycerin, water, hexafluoroisopropanol, and the like, and these are used alone or as a mixture. Further, an aqueous solution of an inorganic salt such as lithium chloride and calcium chloride can be used alone or as a mixture with the organic solvent. Among these, water, dimethyl sulfoxide, a mixed solution of dimethyl sulfoxide and water, glycerin, and ethylene glycol are preferred. The concentration of the PVA solution used during film formation varies depending on the film formation method.
６０60% by weight, and the temperature during film formation is usually from room temperature to 2%.
It is in the range of 50 ° C.

After film formation, if necessary, uniaxial or biaxial stretching or rolling can be performed. The stretching or rolling of the film can be performed by dry heat or wet heat, and the temperature during stretching is usually in the range of room temperature to 270 ° C. Also,
By applying a heat treatment at about 100 to 150 ° C. after film formation, the dissolution rate of the film can be controlled. In addition, in order to improve the anti-blocking property and water solubility of the film, it is preferable to perform matting, embossing and spraying of an anti-blocking agent on the film surface.

The shape and transparency of the film of the present invention are not particularly limited. The thickness of the film is individually determined depending on the type of the pesticide, the amount of the pesticide, the packaging form, the dissolution rate, and the like, but is usually preferably 20 to 100 μm.

The film of the present invention may contain a plasticizer, if necessary. PVA as plasticizer
Polyhydric alcohols are preferred from the viewpoint of compatibility of the system resin.
Among them, glycerin, diglycerin, trimethylolpropane, diethylene glycol, triethylene glycol, dipropylene glycol, and propylene glycol are preferred from the viewpoint of imparting flexibility and biodegradability. As the plasticizer having a small migration property to the film surface, polyethylene glycol, polypropylene glycol, a compound obtained by adding a few moles of ethylene oxide or propylene oxide to a polyhydric alcohol, an esterified product of a polyhydric alcohol and an organic acid, and the like are appropriately used. . Among these, glycerin, trimethylolpropane, and diglycerin are particularly preferred because of the great effect of imparting flexibility. The above plasticizers can be used alone or in combination of two or more. The content of the plasticizer is preferably 5 to 40 parts by weight based on 100 parts by weight of the PVA-based resin.
More preferably, it is 30 parts by weight. If the amount of the plasticizer is less than 5 parts by weight, the flexibility of the film under low temperature and low humidity tends to be insufficient, which may cause breakage of the bag when used for agricultural chemical packaging. From the viewpoint of water solubility, the content of the plasticizer is preferably as large as possible. However, since bleeding may occur, the content is preferably 40 parts by weight or less, more preferably 30 parts by weight or less.

The film of the present invention may contain, if necessary, a material other than the above-mentioned PVA-based resin and plasticizer as long as the effects of the present invention are not impaired. For example, resins other than PVA-based resins; water-soluble polymers such as starch, carboxymethylcellulose, and hydroxymethylcellulose; and inorganic compounds such as clay, silica, and calcium carbonate. If necessary, a stabilizer such as a dye, a pigment, a fragrance, an antioxidant, and an ultraviolet absorber can be contained. In addition, as long as the effects of the present invention are not impaired, there is no problem even if a small amount of a PVA-based resin having a 1,2-glycol bond amount of less than 1.8 mol% is contained.

Agrochemicals that can be packaged with the film of the present invention include:
Chemicals defined by the Agricultural Chemicals Control Law, such as fungi, nematodes, harmful crops (including trees) or agricultural and forestry products
Examples thereof include fungicides, insecticides, herbicides, and other agents used for controlling animals and plants such as mites, insects, rats, and weeds. Specifically, germicidal dispersants such as bordeaux, soil such as chlorpicrin, seed disinfectants, insecticides such as organic phosphorus and DDT, penetrant insecticides such as shuradan, 2,4-
Herbicides such as D (2,4-dichlorophenoxyacetic acid),
Plant growth regulators such as naphthyl acetic acid and the like, as well as other pesticides, attractants, repellents and the like can be mentioned. In addition, a composition in which a developing agent such as talc, kaolin, bentonite, a synergist such as sulfoxide, a surfactant or a dispersant for increasing the affinity of the pesticide to water or dispersing it uniformly is mixed with the pesticide. Are also included in the pesticides of the present invention. As the form of the pesticide, a powdery form, a granular form, and in some cases, a liquid form dissolved in an organic solvent can be packaged and used. Usually, pesticides are packaged with the film of the present invention in units of several grams to several tens of kilograms, stored and transported in a box or an aluminum outer bag, and used directly on site.
Pesticide unit-packaged with the film of the present invention, as a wettable powder to be used by dissolving and using the bag in water beforehand,
Alternatively, various usages are possible as a jumbo agent to be directly injected into a field or a paddy field.

The film of the present invention in which an agricultural chemical is packaged dissolves quickly when put into water. In particular, when used as a wettable powder, a pesticide dispersed and dissolved in water in advance is sprayed, so that there should be no undissolved residue. The rate of dissolution in water, when a film having a thickness of 40 μm, is usually preferably dissolved within 5 minutes after immersion in stirring water at 20 ° C., more preferably dissolved within 2 minutes, and more preferably within 1 minute. More preferably, it is dissolved.

The higher the Young's modulus of the film of the present invention, the more
The stiffness of the film is improved, and processability is improved. Since the Young's modulus changes depending on the 1,2-glycol bond amount of the film, the degree of saponification, the amount of the plasticizer, the heat treatment conditions, and the like, it is necessary to appropriately adjust various conditions. Although the reason is unknown, since the film having the same composition tends to have a higher Young's modulus as the amount of 1,2-glycol bond increases,
The film of the present invention using a PVA-based resin having a 2-glycol bond content of 1.8 mol% or more has good process passability.

Usually, a water-soluble film for packaging agrochemicals is desired to have biodegradability because it is released into nature after use. However, the film of the present invention has excellent biodegradability. It is also an environmentally friendly film. Biodegradation rate of the film of the present invention (25 ° C., 28 days)
Is preferably at least 60%, more preferably at least 80%. It should be noted that the decomposition rate referred to in the present specification is I
It is a biodegradation rate when evaluated according to the biodegradability evaluation method described in SO14851, and specifically, a value measured by the analysis method described in the section of Examples.

[0026]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

[Analysis method of PVA] (1) The analysis method of PVA is JIS-K unless otherwise specified.
Followed 6726. (2) 1,2-glycol bond amount of PVA: First, the PVA-based resin to be measured is saponified to a degree of saponification of 99.9 mol% or more, thoroughly washed with methanol, and then dried under reduced pressure at 90 ° C. for 2 days. after, and dissolved in DMSO-D _6, measured at 80 ° C. using a further trifluoroacetic acid number drops added samples of 500MHz prepared by proton NMR (JOEL GX-500). The peak derived from methine in the vinyl alcohol unit is 3.2 to 4.0 ppm (integral value A),
The peak derived from one methine of the 1,2-glycol bond is assigned to 3.25 ppm (integral value B).
The amount of 2-glycol bond can be calculated. 1,2-glycol bond amount (mol%) = (B / A) × 1
(3) Short-chain branching amount of PVA: A PVA-based resin to be measured is first saponified to a degree of saponification of 99.9 mol% or more, thoroughly washed with methanol, and then dried under reduced pressure at 90 ° C. for 2 days. , DMSO-D ₆ a sample dissolved in in ¹ H NMR of 500MHz, also D ₂ ¹³ samples the 125.65MHz dissolved in O C NMR (JOEL GX-50
Measure at 80 ° C using 0). The peak derived from methine in the vinyl alcohol unit was 3.2 to 4.0 pp from the sample.
m (integral value C), the peak derived from methylene of the terminal alcohol was assigned to 3.52 ppm (integral value D), and the peak derived from methylene of all terminal alcohols was 60.9% from the sample.
5 to 61.65 ppm (integral value E), and the peak derived from methylene of the short-chain branched terminal alcohol is 60.95 to 61.1.
It is assigned to 8 ppm (integral value F), and the content of the short-chain branch can be calculated from the following equation. Short chain branch content (mol%) = [(D / 2) / C] ×
(F / E) × 100

[Measurement method of water solubility] Pour ion-exchanged water into a 500 ml beaker, stir 280 revolutions per minute with a magnetic stirrer, and place 40 m in water set at 20 ° C.
A film cut into a square of mx 40 mm was immersed in a slide mount, and the time (seconds) until the film was completely dissolved was measured and evaluated.

[Biodegradability evaluation method] The biodegradability was evaluated according to the biodegradability evaluation method described in ISO14851.
That is to say, 300 ml of the inorganic medium solution was acclimated to the sludge obtained from the sewage treatment plant on the day of the test and the PVA aqueous solution.
Sludge that has been acclimated for one month is mixed at 1: 1) 30mg
And a sample of 30 mg, add a coulometer (Okura Electric OM
(Type 3001A) was cultured at 25 ° C. for 28 days, and the biodegradation rate was determined by measuring the amount of oxygen consumed for biodegradation.

Example 1 3000 g of vinyl acetate and 0.0 g of tartaric acid were placed in a 5-liter pressurized reaction tank equipped with a stirrer, a nitrogen inlet and an initiator inlet.
After charging 90 g, the reactor pressure was raised to 2.0 MPa while bubbling with a nitrogen gas at room temperature, and the mixture was allowed to stand for 10 minutes. Then, the operation of releasing the pressure was repeated three times to replace the system with nitrogen. A 0.1 g / liter solution of 2,2′-azobis (N-butyl-2-methylpropionamide) dissolved in methanol was prepared as an initiator.
Nitrogen was replaced by bubbling with nitrogen gas. Next, the temperature inside the polymerization tank was raised to 150 ° C. At this time, the reactor pressure was 0.8 MPa. Next, 8.0 ml of the above initiator solution was injected to start polymerization. During the polymerization, the polymerization temperature was maintained at 150 ° C., and 1
At 3.6 ml / hr, 2,2′-azobis (N-butyl-
(2-methylpropionamide) was added continuously to carry out polymerization. The reactor pressure during the polymerization was 0.85 MPa. After 3 hours, the mixture was cooled to stop the polymerization. At this time, the solid content concentration was 25%. Next, unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C., and a methanol solution of polyvinyl acetate (concentration 3
3%). Methanol was added to the obtained polyvinyl acetate solution, and 400 g of a methanol solution of polyvinyl acetate (100 g of polyvinyl acetate in the solution) adjusted to a concentration of 25% was added at 40 ° C. with 11.6 g (polyacetic acid). Molar ratio (MR) to vinyl acetate unit in vinyl
0.025) of an alkaline solution (a 10% methanol solution of NaOH) was added for saponification. The gel that was gelled in about 2 minutes after the addition of the alkali was pulverized by a pulverizer and left for 1 hour to progress the saponification. Then, 1000 g of methyl acetate was added to neutralize the remaining alkali. After confirming the completion of the neutralization using a phenolphthalein indicator, 1000 g of methanol was added to the white solid PVA obtained by filtration and washed at room temperature for 3 hours. After repeating the above washing operation three times, the PVA obtained by centrifugal dewatering was placed in a dryer at 70 ° C.
For 2 days to obtain dry PVA. The degree of saponification of the obtained PVA was 98.0 mol%. After the polymerization, the methanol solution of polyvinyl acetate obtained by removing the unreacted vinyl acetate monomer was saponified at an alkali molar ratio of 0.5, and the pulverized product was left at 60 ° C. for 5 hours to progress the saponification. After that, Soxhlet washing with methanol was performed for 3 days, followed by drying under reduced pressure at 80 ° C. for 3 days to obtain purified PVA. The degree of polymerization of the PVA is determined by a standard JIS
It was 1200 when measured according to K6726.
The amount of 1,2-glycol bond and the amount of short-chain branching of the purified PVA were determined by 500 MHz proton NMR (JEOL GX-50).
0) It was 2.54 mol% and 0.084 mol% when measured by the above-mentioned method using an apparatus. PVA
Are shown in Table 1. An aqueous solution was prepared using 20 parts of glycerin with respect to 100 parts of the obtained PVA.
To obtain a film having a thickness of 40 μm. After film formation, heat treatment was performed at 100 ° C. for 10 minutes. A bag of 10 cm × 20 cm was made from this film, and 40 g of a fine powder of an agrochemical (an insecticide, “Gamba WP” manufactured by Nivaltics Agro, wettable powder) was put therein and sealed by heat sealing. This pesticide packaging bag was further heat-sealed with a film in which aluminum foil was laminated with polyethylene to prevent water and plasticizer from scattering from the pesticide packaging bag. This bag was placed in a constant temperature oven at 40 ° C. as an accelerated test of a long-term storage test, left for one month and three months later, and the change in water solubility of the packaged film was observed over time. The biodegradability was evaluated from a sample sampled from the film after being left for 3 months. The results are shown in Table 2. The obtained film had a firm waist and was excellent in workability. After 3 months at 40 ° C., there was almost no decrease in water solubility, and the biodegradability was good.

Example 2 Polymerization and saponification were carried out in the same manner as in Example 1 except that the polymerization temperature was changed to 180 ° C. The physical properties of the obtained PVA were such that the degree of polymerization was 1,000, the degree of saponification was 98.6 mol%,
2-glycol amount 2.92 mol%, short-chain branching amount 0.12
It was 4 mol%. Table 1 summarizes the physical properties. Example 1
A film was prepared in the same manner as described above, except that the plasticizer was PVA.
The amount was changed to 10 parts of glycerin and 12 parts of diglycerin for 100 parts. The same pesticides as in Example 1 were packaged and an accelerated long-term storage test was performed. Table 2 shows the obtained evaluation results. The packaging bag after the standing test did not leak odor, and had flexibility and excellent film properties.

Example 3 29.4 kg of vinyl acetate and 0.6 kg of methanol were charged into a 50-liter pressure reactor equipped with a stirrer, a nitrogen inlet, an ethylene inlet, an initiator addition port and a delay solution addition port. After the temperature was raised to ° C., the system was replaced with nitrogen by bubbling nitrogen for 30 minutes. Next, the reaction vessel pressure was set to 18.
Ethylene was introduced into the reaction vessel so as to be 0 kg / cm ² . 2,2′-azobis (N-butyl-2) as an initiator
-Methylpropionamide) was dissolved in methanol to prepare a solution having a concentration of 0.1 g / liter, followed by bubbling with nitrogen gas and purging with nitrogen. When the temperature inside the polymerization tank is 1
After the temperature was adjusted to 50 ° C., 45 ml of the above initiator solution was injected to start polymerization. During the polymerization, ethylene was introduced to raise the reaction tank pressure to 18.0 kg / cm ² and the polymerization temperature to 150 ° C.
185 ml / hr using the above initiator solution.
2,2'-azobis (N-butyl-2-methylpropionamide) was continuously added to carry out polymerization. After 3 hours, when the degree of polymerization reached 25%, the polymerization was stopped by cooling. After the reaction vessel was opened to remove ethylene, nitrogen gas was bubbled through to completely remove ethylene. Next, unreacted vinyl acetate monomer was removed under reduced pressure to obtain a methanol solution of ethylene-modified polyvinyl acetate. To 333 g of a methanol solution of ethylene-modified polyvinyl acetate (100 g of polyvinyl acetate in the solution) adjusted to a concentration of 30% by adding methanol to the obtained ethylene-modified polyvinyl acetate solution, 9.3 g (polystyrene) was added. Saponification was performed by adding an alkali solution (10% methanol solution of NaOH) having a molar ratio (MR) of 0.02 to the vinyl acetate unit in vinyl acetate. After about 5 minutes from the addition of the alkali, the gelled system was pulverized with a pulverizer and left at 40 ° C. for 1 hour to progress the saponification. Then, 1000 g of methyl acetate was added to neutralize the remaining alkali. After confirming the completion of neutralization using a phenolphthalein indicator, 1000 g of methanol was added to a white solid ethylene-modified PVA obtained by filtration.
Was added and washed at room temperature for 3 hours. 3
Repeated, and then centrifuged to remove the ethylene-modified P
VA was left in a dryer at 70 ° C. for 2 days to obtain dry ethylene-modified PVA. When the above-mentioned analysis was performed on the obtained ethylene-modified PVA, the degree of polymerization of PVA was 115
0, the degree of saponification was 94.6 mol%, the ethylene modification amount was 3 mol%, the 1,2-glycol bond amount was 2.43 mol%, and the short-chain branching amount was 0.067 mol%. Table 1 summarizes the physical properties. Next, a film was prepared in the same manner as in Example 1, the pesticide was packaged, and an accelerated long-term storage test was performed. Table 2 shows the obtained evaluation results.

Example 4 Polymerization and saponification were carried out in the same manner as in Example 1 except that the polymerization temperature was changed to 120 ° C. The physical properties of the obtained PVA were such that the degree of polymerization was 1620, the degree of saponification was 96.2 mol%,
2.23 mol% of 2-glycol, 0.05 short chain branch
It was 1 mol%. Table 1 summarizes the physical properties. Example 1
A film was prepared in the same manner as described above, and the pesticides were packaged, and an accelerated long-term storage test was performed. Table 2 shows the obtained evaluation results.

Example 5 2400 g of vinyl acetate and 600 ml of methanol were placed in a 5-liter pressurized reaction vessel equipped with a stirrer, a nitrogen inlet, and an initiator inlet.
g and 49.3 g of vinylene carbonate, the pressure in the reaction vessel was increased to 2.0 MPa while bubbling with nitrogen gas at room temperature, and the reaction was allowed to stand for 10 minutes. Replaced.
A 1.0 g / liter solution of α, α'-azobisisobutyronitrile dissolved in methanol as an initiator was prepared, and nitrogen was replaced by bubbling with nitrogen gas. Next, the temperature inside the polymerization tank was raised to 90 ° C. At this time, the reactor pressure was 0.4 MPa. After adjusting the internal temperature of the polymerization tank to 90 ° C., 3.0 ml of the initiator solution was injected to start polymerization. During the polymerization, the polymerization temperature was maintained at 90 ° C., and α, α′-azobisisobutyronitrile was continuously added at 4.9 ml / hr using the above-described initiator solution to carry out the polymerization. The reactor pressure during the polymerization was 0.4 MPa. After 4 hours, the mixture was cooled to stop the polymerization. At this time, the solid content concentration was 38%. Then, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution of vinylene carbonate-modified polyvinyl acetate (concentration: 33%). 40 g of a methanol solution of vinylene carbonate-modified polyvinyl acetate (100 g of polyvinyl acetate in the solution) adjusted to 25% by adding methanol to the obtained vinylene carbonate-modified polyvinyl acetate solution,
At a temperature of 4 ° C., saponification was carried out by adding 46.4 g of an alkali solution (a 10% methanol solution of NaOH) (molar ratio (MR) to vinyl acetate unit in polyvinyl acetate: 0.10). The gel that was gelled in about 1 minute after the addition of the alkali was pulverized with a pulverizer and left for 1 hour to progress the saponification. Then, 1000 g of methyl acetate was added to neutralize the remaining alkali. After confirming the completion of the neutralization using a phenolphthalein indicator, 1000 g of methanol was added to vinylene carbonate-modified PVA as a white solid obtained by filtration and washed at room temperature for 3 hours. After repeating the washing operation three times, the vinylene carbonate-modified PVA obtained by centrifugal elimination was allowed to stand in a dryer at 70 ° C. for 2 days to obtain dried vinylene carbonate-modified PVA. The saponification degree of the obtained vinylene carbonate-modified PVA was 99.5 mol%. Further, a methanol solution of vinylene carbonate-modified polyvinyl acetate obtained by removing the unreacted vinyl acetate monomer after polymerization was saponified at an alkali molar ratio of 0.5, and the pulverized product was left at 60 ° C. for 5 hours. After the saponification was advanced, Soxhlet washing with methanol was performed for 3 hours.
The drying was performed at 80 ° C. for 3 days under reduced pressure to obtain purified vinylene carbonate-modified PVA. The degree of polymerization of the vinylene carbonate-modified PVA was measured according to JIS K6
It was 1250 when measured according to 726. The 1,2-glycol bond amount of the purified vinylene carbonate-modified PVA was determined from the measurement with a 500 MHz proton NMR apparatus as described above, and was 2.50 mol%, the modification amount was 0.6 mol%, and the short-chain branching amount was 0.1 mol%. 043 mol%. Table 1 summarizes the physical property values. Next, a film was prepared in the same manner as in Example 1, the pesticides used in Example 1 were packaged, and an accelerated long-term storage test was performed. Table 2 shows the obtained evaluation results.

COMPARATIVE EXAMPLE 1 Using PVA polymerized at a polymerization temperature of 60 ° C. and having a 1,2-glycol bond content of 1.60 mol%, a polymerization degree of 1200, a saponification degree of 88.0 mol% and a short chain branching amount of 0 mol%. A film was prepared in the same manner as in Example 1, the pesticide was packaged, and an accelerated long-term storage test was performed. Table 2 shows the obtained evaluation results.

Comparative Example 2 Using PVA polymerized at a polymerization temperature of 60 ° C. and having a 1,2-glycol bond content of 1.60 mol%, a polymerization degree of 1000, a saponification degree of 95.0 mol%, and a short chain branching amount of 0 mol%. A film was prepared in the same manner as in Example 1, the pesticide was packaged, and an accelerated long-term storage test was performed. Table 2 shows the obtained evaluation results.

Comparative Example 3 The amount of 1,2-glycol bond polymerized at a polymerization temperature of 60 ° C. was 1.50 mol%, the degree of polymerization was 1100, the degree of saponification was 95.0 mol%, the amount of ethylene modification was 3 mol%, and the amount of short-chain branching was 0. A film was prepared in the same manner as in Example 1 using mol% of PVA,
Pesticides were packaged and accelerated long-term storage tests were performed. Table 2 shows the obtained evaluation results.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

As is clear from the above examples, the film of the present invention has excellent water solubility, excellent chemical resistance to pesticides and biodegradability, and has a firm film.
Excellent workability. On the other hand, as shown in the comparative example,
When a pesticide is wrapped with a film obtained from a PVA-based resin having a 1,2-glycol bond content of less than 1.8 mol%, the water solubility decreases with time due to poor chemical resistance to the pesticide.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shintaro Hikasa 1621 Sazu, Kurashiki-shi, Okayama Prefecture Kuraray Co., Ltd. F-term (reference) 3E086 AB01 AD01 BB72 BB74 BB90 CA29 4F071 AA29 AC05 AE04 AF01Y AH04 BC01

Claims (4)

[Claims] An agrochemical packaging film comprising a polyvinyl alcohol resin having a 1,2-glycol bond amount of 1.8 mol% or more and a saponification degree of 92 to 99.9 mol%. 2. The polyvinyl alcohol-based resin 100
The agricultural chemical packaging film according to claim 1, wherein the plasticizer is contained in an amount of 5 to 40 parts by weight based on parts by weight. 3. The polyvinyl alcohol resin has a short-chain branching of 0.03 mol% or more.
A film for packaging agricultural chemicals according to the above. 4. The biodegradation rate is 60% or more.
4. The film for packaging agrochemicals according to any one of 3 above.