JPH0535182B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a soft vinyl chloride resin film for agricultural use. More specifically, the present invention relates to a soft vinyl chloride resin film for agricultural use that is less likely to adhere to each other when overlapped (excellent non-adhesion) and also has excellent antifogging properties. "Prior Art" In recent years, farmers cultivating useful plants have widely adopted methods of promoting the cultivation of useful plants in greenhouses or tunnels in order to increase profitability. As the covering material for this house or tunnel, vinyl chloride resin film, polyethylene film, ethylene-vinyl acetate copolymer film, polyethylene terephthalate film, etc. are used. Among them, soft vinyl chloride resin films are used the most because they are superior in weather resistance, transparency, heat retention, and strength compared to other synthetic resin films. These coating materials are made by adding a surfactant to the base synthetic resin material to form a film in order to prevent condensed water from adhering to the inner surface of the house or tunnel. . In addition, since soft vinyl chloride resin film is soft and elastic, it has the advantage of being able to be easily stretched into any shape of house or tunnel, but on the other hand, it tends to stick to other films when they overlap. The property of mutual interaction (so-called adhesiveness)
However, it has the disadvantage that it is larger than polyethylene film or ethylene-vinyl acetate copolymer film. If the adhesiveness of the film is high, the efficiency of spreading the film onto the house or tunnel will decrease, and the efficiency of bonding the films together using high-frequency bonding will also decrease, and after spreading the film onto the house or tunnel, There is a problem that the ventilation work inside the building and the work of opening and closing the house or tunnel are reduced. Examples of cases where the soft polyvinyl chloride film exhibits the property of adhering to each other, that is, adhesiveness, are as follows. (1) Adhesion at low temperatures A phenomenon observed when handling soft polyvinyl chloride at relatively low temperatures below 40°C. In this case, no fusion phenomenon is observed. (2) Adhesiveness at high temperatures When soft polyvinyl chloride film is used as a covering material for a house or tunnel, the films may be stacked or bundled outdoors to ventilate the inside of the house or tunnel. ,
Often exposed to direct sunlight. In this case, the film temperature rises to 40-80°C.
At such high temperatures, the films adhere to each other, and in some cases even fuse, and even when the temperature of the films drops, it takes considerable effort to separate them. reach. (3) Adhesion at high temperatures and in wet conditions This is the same phenomenon as in (2), but if stacked or bundled films are exposed to high temperatures while wet, moisture between the films will increase. After evaporation, a severe adhesive phenomenon occurs. Many techniques have been proposed and some have been put into practical use to eliminate the tackiness of such soft vinyl chloride films and make them exhibit non-adhesive properties (improve the non-adhesive properties). For example, a method is known in which a bisamide-based anti-blocking agent such as methylene bislaurylic acid amide or ethylene bis-laurylic acid amide, or a monoamide-based anti-blocking agent such as stearic acid amide is added to the base synthetic resin. The method of forming a film by blending various anti-blocking agents with the base vinyl chloride resin has a problem in that it is difficult to improve the non-stick properties at low temperatures. The reason why a film containing an anti-adhesive agent exhibits an anti-adhesive effect is that the anti-adhesive agent is ejected onto the film surface. Generally, anti-blocking agents are difficult to spray out onto the film surface at low temperatures, and in order to exhibit non-stick properties even at low temperatures, the amount of the anti-blocking agent must be increased. If a large amount of anti-adhesive is added, the anti-adhesive will spray out more at high temperatures, reducing the transparency of the film.Dust will adhere to the film while it is used as a covering material for a house or tunnel, further reducing the transparency. The disadvantage is that the value decreases. According to experiments conducted by the present inventors, it has been observed that when a film is formed by blending a large amount of anti-blocking agent into a base vinyl chloride resin, the antifogging properties of the film surface are reduced. "Problems to be Solved by the Invention" Under such circumstances, the present inventors have found that not only the non-stick properties of the film at low temperatures, but also the non-stick properties at high temperatures and at high temperatures and humidity are improved, and With the aim of providing a high-quality agricultural soft vinyl chloride resin film that also improves the antifogging properties of the film surface, the present invention has been completed as a result of intensive studies. Therefore, the gist of the present invention is that, for 100 parts by weight of vinyl chloride resin, at least (A) 30 to 60 parts by weight of a plasticizer, (B) 0.5 to 5 parts by weight of a nonionic surfactant, and (C) the following: Compound represented by the general formula ()
0.05～3 〃 R ₁ −NHCONH−R ₂ −NHCONH−R ₁
...() [In the formula (), R ₁ means an alkyl group or alkenyl group having 1 to 22 carbon atoms, and R ₂ means an arylene group or an alkylarylene group. ] An agricultural soft vinyl chloride resin film characterized by being formed into a film by blending the following three components. The present invention will be explained in detail below. In the present invention, the vinyl chloride resin includes not only polyvinyl chloride but also copolymers containing vinyl chloride as a main component. Monomers that can be copolymerized with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile,
Examples include vinyl acetate, maleic acid, itaconic acid, acrylic acid, acrylic esters, methacrylic acid, and methacrylic esters. The vinyl chloride resin may be used alone or in a mixture of two or more. The vinyl chloride resin may be manufactured by any of the conventionally known manufacturing methods such as suspension polymerization, emulsion polymerization, emulsion-suspension polymerization, solution polymerization, and bulk polymerization. . The degree of polymerization of the vinyl chloride resin can be selected within the range of 800 to 2,500. The vinyl chloride resin film according to the present invention includes the above vinyl chloride resin, at least a plasticizer as a component (A), a nonionic surfactant as a component (B), and a specific structural formula as a component (C). Contains three ingredients: an anti-tack agent. The plasticizer blended into the vinyl chloride resin as component (A) functions to impart flexibility to the film. Preferred plasticizers in the present invention include, for example, di-n-octyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, didodecyl phthalate,
Phthalic acid derivatives such as diundecyl phthalate; Isophthalic acid derivatives such as diisooctyl isophthalate; Adipic acid derivatives such as di-n-butyl adipate and dioctyl adipate; Maleic acid derivatives such as di-n-butyl maleate; tri-n- Citric acid derivatives such as butyl citrate; Itaconic acid derivatives such as monobutyl itaconate; Oleic acid derivatives such as butyl oleate; Ricinoleic acid derivatives such as glycerin monoricinoleate; Other tricresyl phosphate, epoxidized soybean oil, epoxy Examples include resin plasticizers. These plasticizers may be used alone or in combination of two or more. The amount of these plasticizers to be blended is selected within the range of 30 to 60 parts by weight per 100 parts by weight of the vinyl chloride resin in order to balance the flexibility and strength of the film. The nonionic surfactant blended into the base vinyl chloride resin as component (B) functions to impart antifogging properties to the film. Nonionic surfactants used in the present invention include ether type surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene ether, and fatty acid moieties with polyhydric alcohols. Examples include ester types of esterified products, and ether ester types such as polyoxyethylene ether of glycerin ester and polyoxyethylene ether of sorbitan ester. Examples of suitable nonionic surfactants are shown below. (a) Partial esters of polyhydric alcohols such as sorbitan, sorbitol, mannitan, mannitol, glycerin, diglycerin, etc. and fatty acids having 12 to 22 carbon atoms; (b) Addition of alkylene oxides when the alkylene oxide is ethylene oxide or propylene oxide. Moles are 1 to 20 moles, polyhydric alcohol is sorbitan,
Sorbitol, mannitan, mannitol, glycerin, diglycerin, the number of carbon atoms in the fatty acids
12 to 22 polyoxyalkylene polyhydric alcohol fatty acid esters (c) A mixture of (a) and (b). These mixtures are obtained as mixtures of monoesters, diesters, and triesters of polyhydric alcohols. In general,
Ester mixtures having a composition with a high content of diester components are preferred. When selecting a preferable nonionic surfactant from among these nonionic surfactants, it is important not only that the film produced by blending it into a film exhibits excellent antifogging properties, but also for workability during film production and heat resistance during film production. It is better to comprehensively consider the transparency of the film, etc. The amount of the nonionic surfactant to be blended is selected from the range of 0.5 to 5 parts by weight based on 100 parts by weight of the base vinyl chloride resin. If this amount is less than 0.5 parts by weight, the film will have poor anti-fogging properties, which is undesirable.
If it exceeds 5 parts by weight, the antifogging property will deteriorate, which is not preferable. The base vinyl chloride resin and the compound represented by the general formula () blended as component (C) function to impart non-adhesive properties to the film. In the general formula (), R ₁ is carbon number 1
~22 alkyl groups, meaning alkenyl groups,
R ₂ means an arylene group or an alkylarylene group. Preferred groups as R ₁ include oleyl,
Palmityl, stearyl, etc. can be given,
Preferred groups as R ₂ include tolylene diisocyanate, xylene diisocyanate, methylene bisphenylene isocyanate, and the like. The blending amount of component (C) is 100% of the base vinyl chloride resin.
It shall be selected from within the range of 0.05 to 3 parts by weight. If it is less than 0.05 parts by weight, the film will not be able to sufficiently improve its non-adhesive properties, which is undesirable. If it exceeds 3 parts by weight, the non-adhesive property improvement effect will not gradually increase, and the anti-fogging properties of the reverse film will decrease. Undesirable. The agricultural soft vinyl chloride resin film according to the present invention contains, in addition to the three components (A), (B), and (C), an antistatic agent, an ultraviolet absorber, a stabilizer, and an antioxidant. , a stabilizing aid, a fungicide, an algaecide, a coloring agent, and other various resin additives. Compounds that can be used as antistatic agents include:
Examples include polyoxyethylene alkylamine, polyglycol ether, sodium p-styrene sulfonate, and the like. These antistatic agents can be used alone or in combination of two or more. Examples of compounds that can be used as ultraviolet absorbers include the following. Benzotriazole UV absorber-2-
(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2
-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-
methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-
propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-
butylphenyl)benzotriazole, 2-
(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,
1,3,3-tetramethylbutyl)phenyl]benzotriazole. Benzophenone UV absorber - 2,2'-dihydroxy-4-methoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone , 2-Hydroxy-4-octoxybenzophenone, Salicylic acid-based ultraviolet absorbers - phenyl salicylate, para-octylphenyl salicylate The ultraviolet absorbers can be used alone or in combination of two or more types. Among those exemplified above, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers are particularly preferred. Compounds that can be used as stabilizers include dibutyltin dilaurate, dibutyltin maleate ester, dioctyltin mercaptide, calcium stearate, barium stearate, zinc stearate, calcium laurate, barium ricinoleate, calcium oleate, zinc octoate, etc. I can give it to you. These stabilizers can be used alone or in combination of two or more. Compounds that can be used as antioxidants include:
2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(6-tert-butyl-
(4-ethylphenol), dilaurylthiodipropionate, and the like. These antioxidants can be used alone or in combination of two or more. Compounds that can be used as stabilizing aids include:
Examples include triphenyl phosphite, dioctyl phenyl phosphite, tris(nonylphenyl) phosphite, diphenylisodecyl phosphite, trilauryl trithiophosphite, diphenyl acid phosphite, and dioctyl acid phosphite. These stabilizing aids can be used alone or in combination of two or more. Compounds that can be used as fungicides and algaecides include 2,4,5,6-tetrachloroisophthalonitrile, 10,10'-oxybisphenoxyarsine, 2-(4-thiazolyl)-benz Imidazole, N(fluorodichloromethylthio)phthalimide, N-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)sulfamide, paraoxybenzoic acid ester, 5-bromo-5-nitro-
Examples include 1,3-dioxane, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, 3-methyl-4-chlorophenol, N(tetrachloroethylthio)phthalimide, and tributyltin laurate. These compounds are
They can be used alone or in combination of two or more. Examples of colorants that can be used include phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc white, permanent red, quinacridin, and carbon black.
These colorants can also be used alone or in combination of two or more. The various resin additives mentioned above, including other plasticizers, should be added within a range that does not deteriorate the properties of the film, usually 5 parts by weight per 100 parts by weight of the base vinyl chloride resin.
You can choose within the range of parts by weight or less. The above (A) component, (B) component, to the base vinyl chloride resin,
To blend component (C) and resin additives, the necessary amounts of each may be weighed and a conventionally known compounding machine or mixer such as a ribbon blender, Banbury mixer, super mixer, or the like may be used. In order to form a film from the resin composition obtained in this way, a method known per se can be used, such as melt extrusion molding method (including T-die method and inflation method), calender molding method, solution casting method. Any conventionally known method may be used. If the thickness of the film is too thin, the strength will be insufficient, which is undesirable.On the other hand, if the film is too thick, it will cause inconvenience in the film forming process and subsequent handling (including cutting, gluing, stretching, etc.). 0.03〜
The range is preferably 0.3 mm, preferably 0.05 to 0.2 mm. The agricultural soft vinyl chloride resin film according to the present invention can be used for covering greenhouses, tunnels, etc., and can also be used for mulching. "Effects of the Invention" The present invention has been described in detail above, and has the following particularly remarkable effects, and its industrial utility value is extremely large. (1) The agricultural soft vinyl chloride resin film according to the present invention contains at least the three components (A), (B) and (C) in a specific range, so the film does not bleed.・With little outflow, the film exhibits excellent non-adhesive properties both at low temperatures, at high temperatures, and at high temperatures and humidity. (2) The agricultural soft vinyl chloride resin film according to the present invention contains at least the three components (A), (B) and (C) in a specific range, so the film is excellent. Demonstrates anti-fog properties. "Examples" Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Examples 1 to 5, Comparative Examples 1 to 8 Polyvinyl chloride (=1400)...100 parts by weight Dioctyl phthalate...50 Tricresyl phosphate...5 Epoxy resin (manufactured by Shell Chemical Co., USA, trade name) "EP-828") ...1 Barium stearate ...0.2 Zinc stearate ...0.4 Sorbitan monopalmitate ...1.5 A resin composition was prepared, and the resin composition shown in Table 1 was added to it. The types and amounts of component (B) and component (C) were blended. After stirring and mixing each compound with a super mixer for 10 minutes, kneading it on a mill roll heated to 165°C,
A film with a thickness of 0.1 mm was prepared. Table 1 shows the quality evaluation results for each film. The evaluation and judgment methods for these qualities were as follows. (b) Anti-fogging properties: 13 types of films were spread out in a single-roof greenhouse set up facing south in a test field in Isshi District, Mie Prefecture, and the condition of water droplets adhering to the surface of the film on the house side was observed with the naked eye. Observed. The observation results were displayed as follows. ◎…Water droplets adhering to the film surface (the side facing the inside of the house) coalesce and spread into a thin film, and the area of this thin film portion covers more than 1/2 of the film surface (same as above). 〇…It is observed that water droplets attached to the film surface (same as above) coalesce and spread into a thin film, but the area of this thin film portion is less than 1/2 of the film surface (same as above). Δ: Coalescence of water droplets adhering to the film surface (same as above) is observed, but formation of a thin film-like portion is not observed. ×: Coalescence of water droplets attached to the film surface (same as above) is not observed. (b) Adhesiveness Layer two 30mm x 100mm films and press them with a rubber roll to eliminate air between the films.
Both were brought into close contact. The adhered film was placed in an oven set at a predetermined temperature (40°C, 80°C) and maintained at this temperature for 2 hours. Next, the film was taken out of the oven and left at room temperature for 15 minutes, and then the two films were peeled off using a tensile tester, and the tackiness was measured based on the peel stress at that time. The releasability in a wet state is determined by adding moisture between the two films and adhering them together using the same procedure as above (but at 80°C).
Peeling stress was measured only in the case of .

[Table] From Table 1, the following becomes clear. (1) The films according to the present invention (Examples 1 to 5) are
It has excellent anti-fogging properties and excellent non-stick properties under high temperature and high temperature humid conditions. (2) When the amount of component (B) or component (C) added is less than the range specified in the claims (Comparative Example 1, Comparative Example 4) or more (Comparative Example 7, Comparative Example 2)
In this case, the antifogging properties and/or adhesiveness of the film become inferior. (3) If a compound that does not fall under component (C) is blended as an anti-blocking agent, non-stick properties under high temperature and humidity conditions will be poor.Increasing the blending amount will slightly improve this, but will result in a decrease in anti-fogging properties ( Comparative Example 3, Comparative Example 6, Comparative Example 8).

Claims (1)

[Claims] 1. At least (A) 30 to 60 parts by weight of a plasticizer, (B) 0.5 to 5 parts by weight of a nonionic surfactant, based on 100 parts by weight of a vinyl chloride resin. (C) The following general formula () Compound represented by the formula
0.05～3 〃 R ₁ −NHCONH−R ₂ −NHCONH−R ₁
...() [In the formula (), R ₁ means an alkyl group or alkenyl group having 1 to 22 carbon atoms, and R ₂ means an arylene group or an alkylarylene group. ] A soft vinyl chloride resin film for agricultural use, which is made by blending the following three components and forming it into a film.