JPS6253543B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a vinyl chloride resin composition, and more specifically, a vinyl chloride resin composition for agricultural film molding with excellent anti-fogging durability. It is about things. "Prior Art" In recent years, with the modernization of agricultural crop cultivation, facility cultivation, such as greenhouse cultivation and tunnel cultivation, has become popular. Covering materials used in these cultivations include polyethylene film, polyvinyl chloride film, ethylene-vinyl acetate copolymer film, and various other resin films. Among these, polyvinyl chloride film has excellent heat retention,
It is currently the mainstream coating material because it has excellent transparency, work strength, etc., and is also inexpensive. However, since the vinyl chloride resin film has a hydrophobic surface, when it is spread into a house, water vapor generated inside the house condenses as fine water droplets on the inner surface of the film. For this reason, the condensed water droplets not only significantly reduce light transmission and block sunlight from irradiating cultivated crops, but also fall onto cultivated crops, damaging them.
In some cases, it may cause disease. Conventionally, in order to solve this problem, the inner surface of the vinyl chloride resin film was given hydrophilic properties to uniformly wet the surface, or the water droplets were broken and flowed down, thereby reducing the cloudiness of the inner film surface. In order to prevent this from occurring, antifogging agents have been incorporated into vinyl chloride resin compositions before film molding. Generally known types of antifogging agents include glycerin and fatty acid esters of polyhydric alcohols such as sorbitan. However, when a vinyl chloride resin film is mixed with an antifogging agent, the antifogging agent decomposes and flows out during outdoor greenhouse expansion, and the long-lasting antifogging effect is gradually lost. The long-lasting anti-fogging effect can be improved to some extent by incorporating a larger amount of anti-fogging agent, but on the other hand, it may cause bloom or bleed phenomena on the film surface and may affect the quality, such as poor transparency. Therefore, it could not be said to be a satisfactory method for maintaining the antifogging effect. "Problems to be Solved by the Invention" In view of the current situation, the present inventors obtain a resin composition for molding agricultural vinyl chloride resin films that is comparable in quality and has excellent anti-fogging durability. As a result of intensive studies, we found that a vinyl chloride resin composition containing an antifogging agent and an inorganic basic carbonate has excellent antifogging durability when molded into an agricultural film, and has superior antifogging properties compared to conventional ones. The present invention was developed based on the knowledge that the film is comparable in quality to antifogging agricultural films. "Means for Solving the Problems" That is, the present invention provides a means for solving the problems by adding vinyl chloride resin to vinyl chloride resin.
Vinyl chloride for forming an antifogging agricultural film, characterized by containing 1 to 5 parts by weight of an antifogging agent and 1 to 10 parts by weight of a magnesium-aluminum basic carbonate per 100 parts by weight. The gist is a system resin composition. The present invention will be explained in more detail below. The raw material vinyl chloride resin in the present invention is mainly polyvinyl chloride, vinyl chloride,
Copolymers of this and other monomers, such as vinyl acetate, ethylene, propylene, alkyl vinyl ethers, acrylic esters, methacrylic esters, acrylonitrile, polyvinyl chloride or the above copolymers, chlorinated polyethylene, chlorinated polypropylene, chlorinated polyvinyl chloride, etc. Examples include polymer blends with chlorine-containing polymers or copolymers such as isoprene, but the present invention is not affected in any way by the type and degree of polymerization of the resin. The resin composition according to the present invention contains an antifogging agent as a first component. As the antifogging agent used in the present invention, nonionic, anionic and cationic surfactants are used, such as polyoxyalkylene ether,
Partial ester of polyhydric alcohol, partial ester of alkylene oxide adduct of polyhydric alcohol,
Examples include higher alcohol sulfate ester alkali metal salts, alkylaryl sulfonates, quaternary ammonium salts, and aliphatic amine derivatives. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyoxyethylene sorbitan monolaurate, polyoxypolyethylene sorbitan. Monopalmitate, Glycerin Monolaurate, Glycerin Monopalmitate, Glycerin Monostearate, Glycerin Monooleate, Pentaerythritol Monolaurate, Sorbitan Monopalmitate, Sorbitan Monobehenate, Sorbitan Distearate, Diglycerin Monooleate, Tri Glycerin diolate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalene sulfonate, cetyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dodecylamine hydrochloride, laurylamide ethyl laurate phosphate, triethylcetylammonium iodide , oleylaminodiethylamine hydrochloride, and the basic pyridinium salt of dodecylpyridinium sulfate.
Among them, aliphatic acids with 14 to 22 carbon atoms, sorbitan,
Preferred examples include nonionic surfactants whose main constituents are esters with polyhydric alcohols such as sorbitol, glycerin, polyglycerin, and propylene glycol, or alkylene oxide adducts thereof. The composition according to the present invention contains a magnesium-aluminum basic carbonate as a second component. In the present invention, magnesium-aluminum-based (hereinafter referred to as Mg-Al-based) base carbonate refers to the following compositional formula: Mg _1-x・Alx(OH) ₂ (CO ₃ )〓・mH ₂ O (where O<x< 1, O≦m). A specific example is Kyowa Chemical Industry Co., Ltd.'s Alkamizer 1 (x=0.33,
m=0.5), Alcamizer 2 (x=0.33, m=
0) etc. The average particle size is preferably 10 μm or less, and more preferably 3 μm or less. If the average particle size exceeds 10μ, the strength and transparency of the film will be significantly reduced, making it difficult to use it as an agricultural film. Further, in order to improve the dispersibility of the above-mentioned inorganic substance, it may be treated with a surface treatment agent such as paraffin, aliphatic acid, polyhydric alcohol, titanate coupling agent, silane coupling agent, etc., as the case may be. The present invention provides a vinyl chloride resin composition in which the antifogging agent as a first component and an Mg-Al basic carbonate as a second component are combined in a vinyl chloride resin as a base. It is characterized by
The antifogging agent is blended in an amount of 1 to 5 parts by weight, and the Mg-Al basic carbonate is blended in an amount of 1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin. If the blending ratio of the antifogging agent is less than this range, the obtained agricultural film will have a low original antifogging effect and a low sustained antifogging effect. On the other hand, if the amount exceeds this range, the antifogging durability is improved, but bleeding of the antifogging agent onto the film surface, blooming, etc. will be noticeable, which is not preferable. In addition, if the blending ratio of Mg-Al basic carbonate is less than the above range, the desired effect of the present invention will not be observed, and if it is in a larger amount, the lasting effect of antifogging properties will further improve, but at low temperatures. This is not preferable because it causes a decrease in antifogging properties during the period. The vinyl chloride resin composition for molding an antifogging agricultural film according to the present invention is formulated with a plasticizer, a stabilizer, an organic phosphorite compound, a lubricant, or an anti-blocking agent in an amount depending on the purpose of use. Contains ultraviolet absorbers, antioxidants, light stabilizers, anti-coloring agents, etc. Furthermore, other compounding agents such as antistatic agents, fillers, anti-proofing agents, pigments, dyes, ultraviolet absorbers, etc. may be added as necessary. Specific examples of plasticizers that can be blended in the present invention include di-n-octyl phthalate, di-2-ethylhexyl phthalate, dibutyl phthalate, diisononyl phthalate, butylbenzyl phthalate, dilauryl phthalate, diheptyl phthalate, dimethyl phthalate, and diisodecyl phthalate. , phthalates such as dioctyl phthalate and dicyclohexyl phthalate, adipates such as dioctyl adipate, diisodecyl adipate, diisonyl adipate, dibutyl diglycol adipate, tricresyl phosphate, tris(isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate ate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, tricylyl phosphate and other phosphates, other polyesters, tetrahydrophthalate, azelate,
Examples include separate type, stearic acid type, citric acid type, and trimellitate type. Epoxy plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, and epoxy resins. The epoxy resin used in the present invention is one obtained by the reaction of polyhydric phenols with epichlorohydrin or methylepichlorohydrin, and bisphenol type and novolac type epoxy resins are particularly preferred. In addition, as a bisphenol type epoxy resin, for example, Araldite 502 (manufactured by Ciba Gaiki Co., Ltd.; epoxy equivalent 233~
250), Epicoat 828 (manufactured by Ciel; epoxy equivalent: 184-194), etc. Examples of noholak-type epoxy resins include DEN431 (manufactured by Dow; epoxy equivalent: 172-179), DEN438 (manufactured by Dow; epoxy equivalent: 175).
~182). The amount of these epoxy plasticizers added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin. Examples of the stabilizer include zinc stearate, barium stearate, calcium stearate, and barium ricinoleate.
These additives are added in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin. The organic phosphite compounds used in the present invention include diphenyldecyl phosphite,
Examples include triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tristearyl phosphite, octyl diphenyl phosphite, diphenyl acid phosphite and the like. The amount of these organic phosphite compounds added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin. Usable lubricants or anti-blocking agents include aliphatic acid lubricants such as stearic acid, palmitic acid and mystyric acid; fatty acid amides such as stearic acid amide, palmitic acid amide, methylene bis stearamide and ethylene bis stearamide; lubricant;
Ester lubricants such as butyl stearate, butyl palmitate, or polyethylene wax,
Examples include organic phosphate metal salts such as liquid paraffin, barium monoisodecyl phosphate, calcium diotadecyl phosphate, zinc monooctadecyl phosphate, and zinc diotadecyl phosphate. Examples of usable ultraviolet absorbers include 2
-Hydroxy-4-methoxybenzophenone, 2
-benzophenone ultraviolet absorbers such as hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone; 2-(2′-hydroxy-3′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-
tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-methylphenyl) )-5-Butoxycarbonylbenzotriazole and other benzotriazole-based UV absorbers; salicylic acid ester-based UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-methylphenyl salicylate, p-octylphenyl salicylate, etc. and cyanoacrylate ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate. Furthermore, examples of antioxidants and light stabilizers that can be incorporated include phenolic antioxidants, such as 2,
6-di-tert-butyl-p-cresol, 4,
4'-thiobis-(3-methyl-6-tert-butylphenol), 2,2(4-hydroxyphenyl)propane, 1,1,3-tris-(2-methyl-4-hydroxy-5-tert -butylphenyl)butane, octadecyl-3-(3,5-di-
tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetra-
(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-
dimethylbenzyl) isocyanurate, tris-
(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate; thiodipropionic acid esters, such as -di-n-dodecyl-thiodipropionate, -di-n-octadecyl-thiodipropionate, Aliphatic sulfides and disulfides such as di-n-dodecyl sulfide, di-n-octadecyl sulfide, di-n
-Antioxidants such as octadecyl sulfide;
2,2,6,6-tetramethylpiperidinyl-4
-benzoate, bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1,
2,3,4-tetra(4-carbonyloxy-
2,2,6,6-tetramethylpiperidine)-butane, Tinuvin-Tinuvin-622 (Ciba Geigy)
), LS-944 (manufactured by Ciba Geigy), LA-55
(manufactured by Adeka Argus Chemical Co., Ltd.), such as 2, 2,
Examples include hindered amine light stabilizers containing 6,6-tetramethylpiperidine units. Examples of the antistatic agent include quaternary ammonium salts, amines, imidazolines, amine oxidized ethylene adducts, polyethylene glycols, and sorbitan esters. Examples of the coloring agent include pigments and dyes such as titanium oxide, ultramarine blue, phthalocyanine blue, and quinacridone red. Furthermore, silica, talc, calcium carbonate, etc. can also be blended as fillers. In order to blend plasticizers and resin additives into the base vinyl chloride resin, conventional blending, mixing techniques,
For example, ribbon blender, Banbury mixer,
A method using a super mixer or other compounding machine or mixer can be adopted. In order to manufacture a base film from the above-mentioned vinyl chloride resin composition, ordinary film manufacturing methods such as calendar molding, extrusion molding, inflation molding, etc. can be appropriately employed. The film produced in this way is coated with acrylic resin, fluorine resin, polyolefin resin,
A film of urethane acrylate resin or the like can be formed. From the vinyl chloride resin composition of the present invention, not only transparent antifogging agricultural films, but also matte satin films, semi-matte films, and colored films can be formed, and the thickness of the films depends on strength, production cost, etc. Considering the range of 0.03~0.3mm, preferably 0.05~
0.2mm thick pieces are molded. "Effects of the Invention" As described above, the present invention provides a vinyl chloride resin composition for molding an antifogging agricultural film, which is a combination of a vinyl chloride resin, an antifogging agent, and an Mg-Al basic carbonate. The agricultural film molded from this product has a significantly superior anti-fog retention effect compared to the agricultural film molded from a conventional resin composition containing only an anti-fog agent. Moreover, there is little blow-out phenomenon of the resin additive added to the base resin on the film surface, and in terms of quality such as transparency and coloring, it is comparable to conventional compositions, making it suitable for covering films for greenhouse cultivation. It is extremely useful for manufacturing purposes. "Examples" The present invention will be described in detail below based on Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Examples 1 to 3, Comparative Examples 1 to 7 Vinyl chloride (=1400) 100 parts by weight Dioctyl phthalate 50 Epoxy resin (product name "Ep-828") 3 Ba-Zn composite liquid stabilizer 1.5 Barium stearate 0.2 The basic composition was 〃 Zinc stearate 0.4〃 〃 Ethylene bis stearamide 0.2〃 〃, and an antifogging agent and Mg-Al basic carbonate of the type and amount shown in Table 1 were added to this. After stirring and mixing with a super mixer for 10 minutes, kneading for 7 minutes on a roll heated to 165℃, and using an L-type calender device, the thickness was
A 0.1 mm film was produced. The following evaluation tests were conducted on each film. The results are shown in Table 1. (1) Anti-fogging properties at low temperatures The upper part of a heat insulating container (diameter 15 cm, height 17 cm) filled with 25°C water up to 2/3 of the container capacity was sealed with a sample film, and a cold air circulating low temperature container was placed at 5°C. The film was left standing in a chamber, and the state of water condensation on the inner surface of the film was visually observed over time. The film was evaluated on a scale of 1 to 10, with a score of "1" indicating that the film was completely cloudy due to condensed water droplets, and a score of "10" indicating that the film was completely transparent with no fogging at all. (2) Anti-fog durability A sample film was stretched at an angle of 5° from the horizontal on a thermostatic water bath maintained at 50°C, and the state of water condensation on the film's inner surface was observed over time. It was evaluated on a 10-point scale in the same way as the anti-fog property. (3) Surface condition of the film After the sample film was left indoors for 3 months, the surface was lightly rubbed with a finger and the state of the eruption was observed with the naked eye based on the extent of the marks. The evaluation criteria were as follows. ◎...No gushing (no marks left). 〇...Almost no gushing (slight finger marks). △...Although it is gushing out, it is not sticky. ×...Obviously gushing and extremely sticky. From Table 1, the following becomes clear. (1) The film molded from the vinyl chloride resin composition of the present invention has better antifogging properties, especially the film molded from the resin composition that does not contain Mg-Al basic carbonate. It has excellent fogging persistence, and the surface condition after 3 months is comparable to that of a product containing only an antifogging agent. (2) Even when combined with Mg-Al basic carbonate,
When the blending ratio of the antifogging agent is 1% by weight or less, almost no antifogging effect is observed. In addition, if the blending ratio of Mg-Al basic carbonate is 1% by weight or less,
The anti-fogging effect is not maintained. 【table】

Claims (1)

[Scope of Claims] 1 A vinyl chloride resin containing 1 to 5 parts by weight of an antifogging agent and 1 to 10 parts by weight of a magnesium-aluminum basic carbonate per 100 parts by weight of the resin. A vinyl chloride resin composition for forming an antifogging agricultural film, which is characterized by: 2. Magnesium-aluminum basic carbonate is obtained from the following composition formula Mg _1-x・Alx(OH) ₂ (CO ₃ )〓・mH ₂ O (however, O<x<1, O≦m) A vinyl chloride resin composition for forming an antifogging agricultural film according to claim 1.