JPH032902B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has excellent anti-blocking properties as shown in the results of high-temperature blocking resistance tests, practical long-term blocking tests, etc.; Excellent stain resistance properties; excellent long-term weather resistance properties as shown in the results of practical long-term brown spotting tests, practical long-term heat and cold resistance tests; excellent spreadability properties as shown in the results of practical spreadability tests; It has excellent suitability for long-term continuous use in that it has a well-balanced range of excellent properties such as excellent film forming suitability as shown in the results of sustained heat resistance forming tests, peelability from forming rolls, and transparency tests. Furthermore, the present invention relates to a unique agricultural vinyl chloride resin film that has properties such as improved plasticization efficiency, UV absorber bleed-out prevention properties, and blowout whitening prevention properties. More specifically, the present invention provides a vinyl chloride resin film containing (A) 10 to 60 parts by weight of phthalic acid dinonyl ester (B) 3 to 7 parts by weight of tricresyl phosphate per 100 parts by weight of the vinyl chloride resin. Part by Weight (C) Epoxidized Plasticizer The present invention relates to an agricultural vinyl chloride resin film containing 3 to 7 parts by weight of a ternary composite plasticizer. Conventionally, agricultural vinyl chloride resin films are often used in the form of soft or ultra-soft vinyl chloride resin films containing a relatively large amount of plasticizer, including for the purpose of improving the film's moldability and cold resistance. is normal. On the other hand, although there are differences depending on the type of plasticizer, increasing the amount of plasticizer tends to cause problems such as deterioration of anti-blocking properties, anti-staining properties, spreadability properties, etc., which is difficult to avoid. It is well known that there are some drawbacks, such as the occurrence of whitening phenomenon and the occurrence of ultraviolet absorber bleed-out phenomenon. In the past, many attempts have been made to provide agricultural vinyl chloride resin films that have the above-mentioned incompatible properties by using a relatively large amount of plasticizer, but they are not always satisfactory. The reality is that we cannot provide vinyl chloride resin films. The present inventors have conducted research in order to provide an agricultural vinyl chloride resin film that has various properties that have been difficult to achieve in the past. As a result, a composite plasticizer consisting of a combination of specific plasticizers of different types in a specific range of proportions was found, in particular, 10 to 60 parts of (A) dinonyl phthalate per 100 parts by weight of vinyl chloride resin. weight part,
(B) 3 to 7 parts by weight of tricresyl phosphate and (C)
Epoxidized plasticizer The use of a three-component composite plasticizer consisting of a combination of at least three different types of known plasticizers in an amount of 3 to 7 parts by weight is highly desired for vinyl chloride resin films in agricultural applications. We have discovered that it is possible to provide a unique agricultural vinyl chloride resin film that has properties that are difficult to reconcile. According to the research conducted by the present inventors, the use of the above three-component composite plasticizer provides excellent anti-blocking properties, anti-staining properties, long-term weather resistance properties, and spreadability properties.
It has outstanding suitability for long-term continuous use in that it has a well-balanced combination of excellent properties such as film molding suitability, and it also has improved plasticization efficiency, UV absorber bleed-out prevention properties, and blowout whitening prevention properties. It has been found that it is possible to provide an agricultural vinyl chloride resin film that also has the following properties. Furthermore, in order to prevent problems such as dust accumulation during spreading, which reduces light transmittance, and deterioration of the long-term weather resistance of the film due to bleed-out or runoff of plasticizers and other additives, we have added special coatings to the film surface. For example, a method of coating with acrylic resin is known, but in the agricultural vinyl chloride resin film containing the three-component composite plasticizer of the present invention, there is no industrial method that performs such an additional coating. It has been found that it is also possible to provide a film that does not easily attract dust without causing any disadvantages. Many other additives other than plasticizers that are usually added to vinyl chloride resins, such as stabilizers, stabilizing aids, lubricants, surfactants, antioxidants, antistatic agents, colorants, and ultraviolet absorbers. In a polyvinyl chloride resin multi-component composition in which the above three-component composite plasticizer is present in the coexistence of a fungicide, an anti-mold agent, an algae-proofing agent, etc., and between these three components and other additives. The interaction or influence of these substances is unknown, and the mechanism of action by which the above-mentioned unique properties can be exerted is unknown. However, as will be shown experimentally later in Examples and Comparative Examples, if one of the combined components of the three-component composite plasticizer is omitted or if the amounts of these components are deviated from the range, the above-mentioned compatibility cannot be achieved. In view of the fact that it is difficult to achieve a property that combines difficult properties in a well-balanced manner, the present inventors have proposed that in the above-mentioned polyvinyl chloride resin multi-component composition, these three components interact and cooperate with each other. It is speculated that this is involved in the exertion of the above-mentioned unique properties. Of course, the present invention is not restricted in any way by such speculation. Therefore, an object of the present invention is to provide an improved vinyl chloride resin film for agricultural use. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. In addition to polyvinyl chloride resins, the vinyl chloride resin used in the present invention includes copolymers containing vinyl chloride as a main component, preferably having a vinyl chloride content of about 90% by weight or more, and furthermore, polyvinyl chloride or Examples include blends of vinyl chloride copolymers and chlorine-containing polymers or copolymers such as chlorinated olefin resins. Examples of comonomers with vinyl chloride include comonomers such as vinyl acetate, ethylene, propylene, alkyl vinyl ethers, acrylic esters, methacrylic esters, acrylonitrile, and the like. Multiple types of these can be used.
Further, examples of the chlorine-containing polymer or copolymer used to form the above blend include, for example, chlorinated polyethylene, chlorinated polypropylene, chlorinated polybutene, chlorinated ethylene/propylene copolymer, chlorinated polyisoprene, etc. can be exemplified. These are not limited to one type, but multiple types can be used in combination. In the present invention, the above-mentioned vinyl chloride resin
Contains the following three-component composite plasticizers (A) to (C) per 100 parts by weight. (A) 10 to 60 parts by weight of phthalic acid dinonyl ester, more preferably about 20 to 60 parts by weight, and even more preferably about 30 to about 50 parts by weight. (B) tricresyl phosphate 3 to 7 parts by weight,
Preferably from about 4 to about 6 parts by weight. (C) Epoxidized plasticizer 3 to 7 parts by weight, preferably about 4 to about 6 parts by weight. The average degree of branching of the above (A) dinonyl phthalate can be selected as appropriate, but the average degree of branching is about 2 or less. The use of phthalic acid dinonyl ester is preferred. The degree of branching of nonyl alcohol, which is the constituent alcohol of phthalic acid dinonyl ester, varies depending on the type of alcohol, with n-nonyl alcohol having a degree of branching of 0, and monomethyloctyl alcohol having a degree of branching of 1, In the case of dimethylheptyl alcohol, the degree of branching is 2, and in the case of trimethylhexyl alcohol, the degree of branching is 3. In the present invention, the average degree of branching of phthalic acid dinonyl ester means that the constituent alcohol of the phthalic acid dinonyl ester is a mixed alcohol component containing one or more of the above-mentioned alcohols other than n-nonyl alcohol. It is expressed as the average value obtained by dividing the sum of the values obtained by multiplying the degree of branching of each alcohol by the polymerization fraction of each alcohol by the number of types of alcohol. It is particularly preferable to use (A) phthalic acid dinonyl ester having an average degree of branching of about 2 or less,
If the value exceeds about 2 and is used, it will have an undesirable effect on the advantage of imparting the above-mentioned properties in a well-balanced manner, and for example, it tends to deteriorate plasticization efficiency, cold resistance, etc. It is preferable to choose things. The amount of the above (A) phthalic acid dinonyl ester used is:
The amount is 10 to 60 parts by weight, preferably about 20 to 60 parts by weight, and more preferably about 30 to about 50 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount used is too small outside the above range, it will be difficult to combine the above-mentioned excellent properties in a well-balanced manner, and, for example, a non-negligible deterioration will occur in anti-blocking properties, anti-staining properties, etc. Furthermore, if the amount is too much outside the above range, it will not be possible to provide the above properties in a well-balanced manner, and for example, blocking resistance, stain resistance, film forming suitability properties, etc. will deteriorate. Therefore, it should be selected appropriately. Furthermore, in the present invention, in addition to the above (A), (B) tricresyl phosphate is added to a vinyl chloride resin.
3 to 7 parts by weight per 100 parts by weight, preferably about 4 to about 6 parts by weight, and (C) epoxidized plasticizer in 3 to 7 parts by weight per 100 parts by weight of the vinyl chloride resin. Preferably it contains about 4 to about 6 parts by weight. If the amount of tricresyl phosphate (B) used is too small outside the above-mentioned range, the long-term weather resistance properties will be significantly deteriorated, and the purpose of improvement of the present invention will be lost. Further, if the amount exceeds the above range, the blocking resistance, cold resistance, film forming suitability, etc. will deteriorate, so the tricresyl phosphate (B) is appropriately selected within the above range. Furthermore, if the amount of the epoxidized plasticizer (C) used falls outside the above range and becomes too small, long-term weather resistance properties, film moldability properties, etc. will deteriorate, and if it falls outside the above range and becomes excessive, anti-blocking properties,
The amount of the epoxidized plasticizer is appropriately selected within the above range since stain resistance, cold resistance, film molding suitability, etc. are reduced. In the present invention, the above three-component composite plasticizer (A), (B) and (C) is 40% by weight per 100 parts by weight of vinyl chloride resin.
It is preferred to use an amount in the range of -70 parts by weight. That is, in addition to the essential condition of satisfying the above-mentioned amount range of each (A), (B) and (C) plasticizer per 100 parts by weight of vinyl chloride resin, these (A), (B) and (C) ) It is necessary to satisfy the conditions that the total amount of plasticizer is 40 to 70 parts by weight per 100 parts by weight of the vinyl chloride resin. It is unique in that it has excellent suitability for long-term continuous use in that it has a good balance of excellent properties such as suitability, and also has properties such as plasticization efficiency, UV absorber bleed-out prevention property, and blowout whitening prevention property. This gives favorable results in providing agricultural vinyl chloride resin films. The three-component composite plasticizer for agricultural vinyl chloride resin films used in the present invention further has a weight ratio of (A):(B) of 1:1/5 to 1/10; It is more preferable that the weight ratio of :(C) satisfies a weight ratio of 1:1/5 to 1/10. The epoxidized plasticizer (C) used in the present invention includes epoxidized plasticizers and liquid epoxy resins that are epoxidized with the double bonds of unsaturated fatty acid compounds such as natural oils and fats and fatty acid esters. Epoxidized plasticizers can be mentioned, and these can also be used in combination. Specific examples of the former type of epoxidized plasticizer include, for example, epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized linseed oil fatty acid butyl, octyl epoxy stearate, epoxy butyl stearate, epoxy hexa Hydrophthalic acid di-2
Examples include -ethylhexyl, diisodecyl epoxyhexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, decyl oleate ester, epoxy diisooctyl tetrahydrophthalate, and the like. Examples of the latter type of epoxidized plasticizer include low molecular weight reaction product resins of epihalohydrins such as epichlorohydrin and bisphenols such as bisphenol A and/or polyhydric alcohols; Low molecular weight epoxy resins that are liquid at room temperature can be preferably used. Both the former type of epoxidized plasticizer and the latter type of epoxidized plasticizer,
Multiple types of each may be used in combination, and as mentioned above, the former and latter types of epoxidized plasticizers can also be used together. In the agricultural vinyl chloride resin film of the present invention, at least
Contains a ternary composite plasticizer containing three components (A), (B), and (C). These plasticizer components (A), (B), and (C) are, for example, stabilizers, stabilizing aids, lubricants, surfactants, antioxidants, antistatic agents, colorants, ultraviolet absorbers, and For vinyl chloride resins for forming agricultural vinyl chloride resin films such as fungicides and algaecides,
Under the conditions of coexistence with other additives that can be blended, what kind of interaction occurs in the vinyl chloride resin, and the effects of blocking resistance, stain resistance, long-term weather resistance, etc.
It has a good balance of excellent properties such as film moldability, and also has improved plasticization efficiency and
Although the mechanism by which it is possible to provide a unique agricultural vinyl chloride resin film that also has UV absorber bleed-out prevention properties and blow-out whitening prevention properties is unknown, it was later compared with examples. As shown by example, any one of the above (A) phthalic acid dinonyl ester, (B) tricresyl phosphate, and (C) epoxidized plasticizer may be omitted, or the amount of each of these components used may be In view of the fact that if the amount substantially deviates from the range, it will be difficult to maintain the excellent properties described above in a well-balanced manner, these three-component composite plasticizer components A and B
It is presumed that C and C interact or influence each other and are involved in imparting unique characteristics to the film of the present invention. The agricultural vinyl chloride resin film of the present invention is
In addition to the three-component composite plasticizer, an amount that does not have a negligible adverse effect on the improvement effect of the film of the present invention, for example, per 100 parts by weight of vinyl chloride resin,
Up to about 30 parts by weight of other plasticizers may be included. Examples of such other plasticizers include dioctyl phthalate, dioctyl adipate, dibutyl phthalate, dinonyl adipate, and the like. These can be used alone or in combination. The agricultural vinyl chloride resin film of the present invention may also contain, for example, a surfactant (antifogging agent), an antistatic agent,
It can contain lubricants, stabilizers, antioxidants, stabilizing aids, colorants, ultraviolet absorbers, fungicides, algaecides, and the like. Examples of such surfactants (antifogging agents) include sorbitan fatty acid ester, sorbitol fatty acid ester, diglycerin fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid/dibasic acid ester, sorbitol fatty acid/dibasic acid ester, and dibasic acid ester. Examples include glycerin fatty acid/dibasic acid esters, glycerin fatty acid/dibasic acid esters, and compounds obtained by condensing these with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. Among these antifogging agents,
Esters of _C12 - _C22 , more preferably _C16 - _C22 fatty acids and dibasic acid esters thereof are preferred. These surfactants can be used alone or in any combination. Specific examples of such surfactants include sorbitan palmitate, sorbitan stearate, polyoxyethylene (3 mol) sorbitan stearate, polyoxypropylene (2 mol) sorbitan palmitate, sorbitol stearate, polyoxy(3 mol) Mol) sorbitol stearate, diglycerin palmitate, diglycerin stearate,
Oxypropylene (1 mol) stearate, glycerin stearate, polyoxyethylene (2 mol) glycerin palmitate, oxypropylene (1 mol) sorbitan stearate adipate, polyoxypropylene (3 mol) polyoxyethylene (5 mol) ) Sorbitol stearate adipate, polyoxypropylene (2 moles) diglycerin palmitate sebacate,
Polyoxypropylene (3 mol) Sorbitol
Examples include palmitate and adipate. The amount of the above-mentioned surfactant to be used can be selected as appropriate, and a preferred example is about 1 to about 2 parts by weight per 100 parts by weight of the vinyl chloride resin. Furthermore, examples of the above-mentioned antistatic agent include antistatic agents such as polyoxyethylene alkylamine, polyglycol ether, sodium p-styrene sulfonate, and the like. The amount of such an antistatic agent to be used can be selected as appropriate, and for example, about 0.1 to about 2 parts by weight per 100 parts by weight of the vinyl chloride resin can be exemplified. In addition, the agricultural vinyl chloride resin film of the present invention can be applied to waxes such as polyethylene wax and liquid paraffin; fatty acids such as stearic acid, oleic acid, and palmitic acid; It may contain lubricants such as fatty acid amides such as acid amides; fatty acid esters such as butyl stearate and methyl hydroxystearate. The amount of such lubricant to be used can be selected as appropriate, but for example, about 100 parts by weight of vinyl chloride resin.
An example of the amount used is about 0.1 to about 1 part by weight. Further examples of stabilizers include, for example, dibutyltin dilaurate, dibutyltin maleate ester,
Organotin stabilizers such as dioctyltin mercaptide; metal soap stabilizers such as calcium stearate, barium stearate, zinc stearate, cadmium stearate, calcium laurate, barium ricinoleate, calcium oleate, zinc octoate; Examples of stabilizers include: The amount of such stabilizer to be used can be selected as appropriate, but for example, about 100 parts by weight of vinyl chloride resin.
Examples include amounts of 0.1 to about 4.0 parts by weight. Examples of antioxidants include 2,6-
di-t-butyl-4-methylphenol, 2,
Examples include antioxidants such as 2'-methylenebis(6-t-butyl-4-ethylphenol) and dilaurylthiodipropionate. The amount of such antioxidant to be used can be selected as appropriate; for example,
An example of the amount used is about 0.1 to about 1.0 parts by weight per 100 parts by weight of the vinyl chloride resin. Furthermore, examples of stabilizing aids include triphenyl phosphite, dioctyl phosphite, tris(phenylphenyl) phosphite, trilauryl trithiophosphite, and the like. The amount used can be selected as appropriate, for example, from about 0.1 to about 100 parts by weight of vinyl chloride resin.
An example usage amount is 2.0 parts by weight. Furthermore, examples of colorants include phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc white, permanent red, carbon black, and quinacridone. The amount used can be selected as appropriate, for example, from about 0.001 to about 5.0 parts by weight per 100 parts by weight of the vinyl chloride resin. The agricultural vinyl chloride resin film of the present invention is
Furthermore, it can contain an ultraviolet absorber. One of the preferred embodiments is an ultraviolet absorber that can prevent the transmission of ultraviolet rays including near ultraviolet wavelengths of 380 nm or less. Examples of such ultraviolet absorbers include 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)-
2'-hydroxyphenyl-5-chlorobenzotriazole UV absorbers such as 5-chlorobenzotriazole; for example, 2-(2'-hydroxy-
3′,5′-di-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[2′-hydroxy-5′-(1,1,3,3 -2'-Hydroxyphenylbenzotriazole-based UV absorbers such as [tetramethylbutyl)phenyl]benzotriazole; for example, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-
4,4'-dimethoxybenzophenone, 2,2',
2,2'-dihydroxybenzophenone ultraviolet absorbers such as 4,4'-tetrahydroxybenzophenone; for example, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, etc. -Hydroxybenzophenone type UV absorbers; for example, cyanoacrylate type UV absorbers such as 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate; for example, salicylic acid ester type UV absorbers such as phenyl salicylate Agents; etc. can be exemplified. Among these ultraviolet absorbers, benzophenone-based and benzotriazole-based ones are more preferred. Among the benzophenones, 2,2'-hydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone and 2,2',4,4'-tetrahydroxybenzophenone; in benzotriazole series, 2-
(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5,6-dichlorobenzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl) ) benzotriazole, 2-(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)
Benzotriazole, 2-(2'-hydroxy-3',
5'-di-tert-butylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-
5'-Phenylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) )-5-chlorobenzotriazole, 2-(2'-
hydroxy-3'-tert-butyl-5'-methylphenyl)-5,6-dichlorobenzotriazole,
2-(2'-hydroxy-3'-tert-butyl-5'-isobutylphenyl)benzotriazole, 2-
(2'-hydroxy-5'-octoxyphenyl)benzotriazole and the like are more preferred. Particularly suitable UV absorbers have the formula

[Formula] or In the formula, R ₁ and R ₂ are the same or different and each represents a hydrogen atom, a lower alkyl group or an aryl group (especially a phenyl group), and R ₁ is particularly preferably a branched or chain-like group having C ₅ or less. It is a lower alkyl group, a hydrogen atom, or a phenyl group, R ₃ is a C ₆ or more alkyl group, especially a C ₈ to C ₁₀ alkyl group, and X is a benzotriazole derivative represented by a hydrogen atom or a halogen atom, especially a chlorine atom. be. The blending amount of the ultraviolet absorber as mentioned above depends on the type of ultraviolet absorber, the type of vinyl chloride resin used,
It can be suitably changed over a wide range depending on the thickness of the film or sheet, the shape of the molded product, etc., but it is about 0.5 to about 100 parts by weight of vinyl chloride resin.
An example of the amount used is about 2.5 parts by weight.
The three-component composite plasticizer used in the present invention has good compatibility with the ultraviolet absorber, has good persistence and stability against light exposure, and can provide an excellent ultraviolet shielding effect. Furthermore, examples of fungicides and algaecides include 2,4,5,6-tetrachloroisophthalonitrile, 10,10'-oxybisphenoxyarsine, and 2-(4-thiazolyl). -benzimidazole, tributyltin laurate, N(fluorodichloromethylthio)phthalimide, N-dimethyl-
N′-phenyl-(N′fluorodichloromethylthio)
- Sulfamide etc. can be exemplified. The amount used can be selected as appropriate, for example, vinyl chloride resin 100%
Examples include amounts of about 0.001 to 3.0 parts by weight. The agricultural vinyl chloride resin film of the present invention is
It can be produced by forming a resin composition containing a vinyl chloride resin, a three-component composite plasticizer, and other compounds into a film using any film-forming method known per se. Examples of such film forming methods include melt extrusion, solution drooling, calendaring, and blow molding. Furthermore, the agricultural vinyl chloride resin film of the present invention (a term that includes agriculture, horticulture, and forestry) can be used in any form in a wide range of agricultural applications, such as for vinyl greenhouses and tunnel cultivation. , for mulching,
It can be used for bag hanging and various other usage forms. Hereinafter, the excellent properties of the agricultural vinyl chloride resin of the present invention will be explained by examples as well as comparative examples.
More specifically, several embodiments will be shown. In addition, the test method and evaluation in the following examples are as follows. (i) Anti-blocking properties. (A) Blocking resistance test at high temperature (50℃): - In a glass test tube (15φ x 150m/m), 50×
A test film cut to 300m/m was wound up while applying a 1.0Kg load to one end, placed in a beaker filled with water at the bottom, placed in a desiccator, and heated to 100C in an electric incubator at 50℃. % for one week, take it out, dry it in an electric incubator at 50°C, and then cool it to room temperature. Attach sellotape to the end of the wound film, attach a weight to the sellotape, and gently rotate the test tube in the direction in which the film will be unwound. If the weight load does not cause unwinding, apply a heavier load. The test was repeated by replacing the weight with a weight of
Measure and show the measured value. The smaller the value, the better the blocking resistance at high temperatures. (B) Practical long-term blocking test: - A test film is coated on a tunnel in a house kept at a maximum temperature below 40°C, and after being left for one day, the coating is removed and a test is conducted while the tunnel remains moist with water droplets. The films were folded and stacked in a greenhouse, left overnight, and then unfolded to observe the degree of blocking.The evaluation was as follows. Evaluation 5... No blocking observed 4... Very slight blocking observed 3... Little blocking 2... Somewhat strong blocking 1... Strong blocking (i) Anti-fouling properties. (A) High temperature (50℃) stain resistance test: - A test film of 60 x 60 m/m is pasted on a glass plate using double-sided adhesive tape, and approximately 35 g/ ^m2 of talc ( Sprinkle evenly over the glass plate (manufactured by Wako Kayaku Co., Ltd., reagent grade 1), place it in an electric incubator at 50°C for 3 days, then take it out and cool it to room temperature. Next, tilt the glass plate at 30°.
Pour water at 20/m ² for about 1 minute from a height of about 30 cm using a Jiro, and then place it in an electric incubator at 50℃ for about 1 minute.
Allow time to dry, then cool to room temperature. Next, cut this film into a size of 20 x 40 m/m and use an integrating sphere turbidity meter (manufactured by Nippon Seimitsu Kogaku Co., Ltd., model SEPT).
Diffuse transmittance and total transmittance were measured, and haze (turbidity) was determined using the following formula. Haze (%) = Diffuse transmittance/Total transmittance x 100 The smaller the haze value, the less dirt there is. (B) Actual long-term stain resistance test: - Using an outdoor test house with a width of approximately 3 m, a depth of approximately 1.5 m, a ridge height of approximately 1.5 m, and a roof slope of approximately 30°, the roof was 50 cm long in the ridge direction and the roof slope was The test film was constructed to form multiple wooden frames (spans) each 1.2 m in length, and the test film stretched over the central span was left outdoors under natural conditions for 2 months and the staining was measured. The amount of solar radiation inside and outside the film was measured using a Minolta digital illuminance meter T-1, and the actual value inside the house was calculated as a percentage of the actual value outside the house.
The larger the percentage, the less dirt there is. (iii) Long-term weathering properties. (A) Actual long-term brown spot development test: - Using a south-facing outdoor test house with a width of approximately 3 m, depth of approximately 1.5 m, ridge height of approximately 1.5 m, and a roof slope of approximately 45°.
The roof was constructed to form multiple wooden frames (spans) with a length of 50 m in the ridge direction and a roof slope length of 1.2 m, and the test film stretched over the central span was tested from July to March of the following year. The samples were exposed outdoors for 9 months and evaluated by visual observation. The evaluation was performed as follows. 5 No brown spots 4 Very few brown spots observed 3 ″ Few 2 ″ Many 1 ″ Very many In addition, the higher the evaluation value, the better the long-term weather resistance. (B) Practical Long-term heat and cold resistance test: - The film after being subjected to the actual long-term brown spotting test in (A) above (exposed outside the roof for 9 months) was subjected to the punch-type impact test method at -15℃. Tester (capacity 30Kg/cm impact velocity
Impact strength was measured using a 2.2 m/sec impact sphere (1 inch radius). In addition, the low-temperature impact strength is practically 100Kg-cm/mm.
or more, preferably 120Kg-cm/mm or more,
Excellent long-term heat and cold resistance. (iv) Expandability properties. (A) Practical stretching suitability test: - The difficulty level of rolling a 3m wide paper tube-wound film into a 10 tsubo pipe house with a height of 2.7m, width of 4.6m and length of 6.7m by 5 members is as follows. The work hours were evaluated. First, attach the film to the side and gable parts of the house, and use a house patch car to secure it at 20 locations in total. Next, use double-sided tape to attach two pieces of film for spreading on the ceiling of the house to make a film approximately 6m wide.
Attach this film to the ceiling and
Stop at 20 locations with a house patrol car. The working time required for this was measured. It should be noted that the shorter the time, the better the spreadability. (v) Film formability properties. (A) Sustained heat-resistant moldability test: - The film material composition was kneaded for 8 minutes in a 170°C test calendar to prepare a film sample with a thickness of 0.1 m/m. This film was subjected to a heat resistance test using a gear oven at 190°C. The time until the film darkened was measured. The longer the time, the better the sustained heat resistance and the better the suitability for film forming. (B) Peelability and transparency test from forming roll: - The film material composition was kneaded for 10 minutes with a test roll at 170°C, and the peelability and transparency between the test roll and the molded sheet (thickness approximately 0.3 m/m) were tested. Check sheet transparency and evaluate according to the following criteria. ○ Both peelability and transparency are good. △ Poor peelability or transparency. × Poor peelability and transparency. (vi) Others (A) UV absorber bleed-out prevention property: - The film sample was suspended in a constant temperature and humidity chamber adjusted to a temperature of 50°C and a relative humidity of 50%, and the UV absorption of the surface was maintained for two weeks. A chemical bleed-out test was conducted. For evaluation, remove the film, observe its appearance,
It went like this: ○ There is no change compared to the time of manufacture × The added ultraviolet absorber is blown out white on the surface and crystallization can be seen. (B) Blow-out whitening prevention property: - The film sample was suspended in a constant temperature and humidity chamber adjusted to a temperature of 50° C. and a relative humidity of 50%, and a surface blow-out test was conducted continuously for two weeks. The evaluation was carried out as follows by taking out the film and observing its appearance. 5 A state in which the surface is transparent and no white powder is observed, similar to the film at the time of manufacture. 4 A state in which white powder is slightly precipitated in a striped pattern. 3 A state in which a thin white layer covers almost the entire surface. 2 A state in which a thin white layer covers the entire surface 1 A state in which a viscous oily substance is gushing out over the entire surface. (C) Plasticization efficiency: −2− to 100 parts by weight of vinyl chloride resin
Using 50 parts by weight of ethylhexyl phthalate (DOP) as a standard, it is expressed as the modulus value of each plasticizer at 100% elongation at 20°C. The smaller the modulus value, the better the plasticizing efficiency. Table 3 Plasticizer type 100% modulus value DOP 1.00 DNP (branching degree approx. 1.3) 1.02 DNP (branching degree approx. 2.0) 1.07 DNP (branching degree approx. 3.0) 1.15 From Table 3, dinonyl phthalate (DNP) of the present invention
The plasticization efficiency with a branching degree of 2.0 or less is better than dinonyl phthalate, which has a branching degree of about 3.0, and is almost the same as DOP. Example 1 Dinonyl phthalate [DINP] with an average degree of branching of about 1.3 is used as a plasticizer for 100 parts by weight of polyvinyl chloride [PVC (1300)] with an average degree of polymerization () 1300.
[Manufactured by Shin Nippon Chemical Co., Ltd.; Sarisocizer DINP] 40 parts by weight and epoxidized soybean oil [Adeca Argus Chemical
Manufactured by Adekasizer O-130P] 5 parts by weight, tricresyl phosphate [TCP] [Daihachi Chemical Co., Ltd.]
manufactured by TCP] 5 parts by weight, barium as a stabilizer.
Zinc composite stabilizer [BZ-300J] 2.0 parts by weight, barium stearate [Ba-St] 0.3 parts by weight, zinc stearate [Zn-St] 0.5 parts by weight, 2,6-di-t-butyl as an antioxidant -4-Methylphenol [BHT] 0.1 part by weight, as a lubricant, 0.3 parts by weight of ethylene bisamide, as a surfactant, 1.5 parts by weight of sorbitan monostearate, polyoxyethylene (2 mol) sorbitan monostearate
0.5 parts by weight, 2-(2'-hydroxy-3',5'-di-t-butyl-phenyl)-5 as an ultraviolet absorber
-Chlorobenzotriazole [Tinuvin 327] 1.0
Parts by weight were blended and kneaded for 8 minutes using a 170°C test calender to prepare a film sample with a thickness of 0.1 mm.
Various tests were conducted on this film sample, and the results are shown in Table 1. Example 2 Under the same conditions as Example 1, 40 parts by weight of dinonyl phthalate with an average degree of branching of about 1.3 was added to 30 parts by weight of dinonyl phthalate with an average degree of branching of about 1.3 and 10 parts by weight of di-2-ethylhexyl phthalate (DOP). Other than changing
A 0.1 mm film was prepared in exactly the same manner. Various tests were conducted on this film sample, and the results are shown in Table 1. Regarding Table 2, in the same manner as in Example 1, each film material formulation of the present invention was heated to a thickness of 0.1 m/m using a test calender according to the formulation in Table 2.
A film sample was prepared. Various tests were conducted on this film sample, and the results are shown in Table 2. Similarly to Example 1, samples of Examples 3 to 7 and Comparative Examples 1 to 4 were prepared according to the descriptions in Tables 1 and 2, and each test was conducted on each sample. The results are shown in Tables 1 and 2. Shown in 2.

【table】

【table】

【table】

[Table] As shown in Tables 1 and 2, suitability for long-term continuous use in terms of film molding suitability, cold resistance, weather resistance, etc., which were previously incompatible, as well as blocking resistance,
Composite plasticizers whose spreadability and stain resistance consist of a combination of specific plasticizers in a specific range, especially per 100 parts by weight of vinyl chloride resin, at least one of dinonyl phthalate, tricresyl phosphate, and epoxidized soybean oil. It can be seen that by using the three types in combination, an agricultural vinyl chloride film having all of the above properties can be obtained. It can be seen that if one component is omitted from the combination of the above three components, it is difficult to achieve both. Furthermore, compared to conventional films, the film of the present invention has good compatibility and can contain a large amount of ultraviolet absorber that improves weather resistance, and has good retention of its ultraviolet absorption rate, particularly for long-term use. It is suitable as an agricultural film for spreading and has extremely high utility value.

Claims (1)

[Scope of Claims] 1. In the vinyl chloride resin film, per 100 parts by weight of the vinyl chloride resin, (A) phthalic acid dinonyl ester 10 to 60 parts by weight (B) Tricresyl phosphate 3 to 7 parts by weight Part (C) Epoxidized Plasticizer An agricultural vinyl chloride resin film characterized by containing 3 to 7 parts by weight of a ternary composite plasticizer. 2. The film according to claim 1, wherein the film contains 0.5 to 2.5 parts by weight of an ultraviolet absorber per 100 parts by weight of the vinyl chloride resin. 3. The film according to claim 1, wherein the content of the three-component composite plasticizer is 40 to 70 parts by weight per 100 parts by weight of the vinyl chloride resin. 4. The film according to claim 1, wherein the weight ratio of (A):(B) is 1:1/5 to 1/10. 5. The film according to claim 1, wherein the weight ratio of (A):(C) is 1:1/5 to 1/10. 6. The film according to claim 1, wherein the average degree of branching of the dinonyl phthalate (A) is about 2 or less.