JPH07157617A - Vinyl chloride resin composition for agricultural use - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride resin composition excellent in long-term weatherability and useful for making agricultural greenhouses and tunnels that can be used in a spread state over a long period of time. CONSTITUTION:100 pts.wt. vinyl chloride resin is mixed with 20-90 pts.wt. plasticizer, 0.01-10 pts.wt. pentaerythritol diphosphate compound represented by the formula (wherein R1 and R2 are each an alkyl or aryl group which may be substituted), and 0.1-5 pts.wt. antifogging agent to give the objective composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural vinyl chloride resin composition, and more specifically to the addition of a specific pentaerythritol diphosphate compound to a vinyl chloride resin in combination with a plasticizer and an antifog agent. Therefore, the present invention relates to an agricultural vinyl chloride resin composition used for agricultural houses and tunnels that can be used for a long period of time.

[0002]

2. Description of the Related Art Vinyl chloride resins are used for a wide range of applications because they are characterized by excellent weather resistance, high strength, and good transparency. In particular, soft products obtained by blending a vinyl chloride resin with a plasticizer are easy to process and are widely used as films and sheets for agricultural houses and tunnels.

However, the vinyl chloride resin is inferior in stability to heat and light, and has a drawback that it tends to undergo thermal decomposition mainly due to dehydrochlorination during heat molding. Also, when used for agricultural purposes such as houses or tunnels, it is used outdoors, so problems such as deterioration of color tone, deterioration of strength, and deterioration of transparency due to the effects of sunlight, dust, oxygen, etc. , Often impaired its practicality.

Conventionally, various heat stabilizers and weather resistance stabilizers have been used in order to improve the heat stability and weather resistance of a vinyl chloride resin during heat molding.

As these heat stabilizers, organic carboxylic acid metal salts (metal soap), organic phosphoric acid metal salts, organic phosphite compounds, epoxy compounds and the like are known.

Further, as the weather resistance stabilizer, various UV absorbers such as benzophenone type and benzotriazole type,
A hindered amine-based light stabilizer represented by a 2,2,6,6-tetramethylpiperidine derivative is known.

By using these light stabilizers, the initial weather resistance of the resin composition is improved to a relatively satisfactory level, and the benzophenone-based and benzotriazole-based UV absorbers are particularly effective. In addition, it has been reported that the effect of preventing the occurrence of diseases can be obtained by cutting off the ultraviolet absorbent having a harmful wavelength, and it has been carried out to add a relatively large amount of the ultraviolet absorbent.

However, these ultraviolet absorbers cannot easily act effectively for a long period of time because they easily bleed or bloom to the resin surface and are extracted by rainwater or the like. Therefore, it has been strongly desired to develop an agricultural vinyl chloride resin composition capable of maintaining weather resistance for a long period of time.

Therefore, an object of the present invention is to improve the practical use of vinyl chloride for agricultural use, which is excellent in weather resistance for a long period of time and can be stretched and used for a long period of time. The purpose is to provide a resin composition.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that vinyl chloride obtained by adding a specific pentaerythritol diphosphate compound to a vinyl chloride resin in combination with a plasticizer and an antifogging agent. It was found that the resin composition can achieve the above object.

The present invention has been made based on the above-mentioned findings. 100 parts by weight of vinyl chloride resin and (a) plasticizer 2
0 to 90 parts by weight, (b) 0.01 to 10 parts by weight of the pentaerythritol diphosphate compound represented by the general formula (I) represented by the following [Chemical formula 2] (the same as the above [Chemical formula 1]), and (c) the protective agent. The present invention provides a vinyl chloride resin composition for agriculture, which comprises 0.1 to 5 parts by weight of a clouding agent.

[0012]

[Chemical 2]

The agricultural vinyl chloride resin composition of the present invention will be described in detail below.

The vinyl chloride resin used in the present invention includes polyvinyl chloride homopolymer and vinyl chloride-
Vinyl acetate copolymer, vinyl chloride-ethylene copolymer,
Vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride- Alkyl, cycloalkyl or alkylmaleimide copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride -Vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-
Examples thereof include vinyl chloride copolymers such as methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers and vinyl chloride-urethane copolymers.

The vinyl chloride resin used in the present invention may be a blend with the following polymer. Examples of the polymer include α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, ethylene-vinyl acetate copolymer, ethylene-
Polyolefins such as propylene copolymers and their copolymers, polystyrene, acrylic resins, copolymers of styrene with other monomers (eg, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers Examples thereof include polymers, methacrylic acid ester-butadiene-styrene copolymers and polyurethanes.

Examples of the plasticizer as the component (a) used in the present invention include dibutyl phthalate, butyl benzyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate and dioctyl terephthalate. Phthalates; Dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate, and other adipate systems; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate. , Trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphe Phosphate-based, such as Ruhosufeto like; polyester, tetrahydropyran phthalate, azelates system, sebacate-based, stearic acid-based, citric acid, trimellitate, and a plasticizer, such as epoxy. Of these, it is preferable to use a phthalate-based or phosphate-based plasticizer, and particularly when both are used in combination, a remarkable effect is recognized.

The amount of the component (a) added is 20 to 90 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the vinyl chloride resin. When the phthalate-based and phosphate-based plasticizers are used in combination, it is generally preferable to add 20 to 70 parts by weight of the phthalate-based plasticizer and 1 to 20 parts by weight of the phosphate-based plasticizer.

The component (b) used in the present invention is a pentaerythritol diphosphate compound represented by the above general formula (I). In the general formula (I), examples of the alkyl group represented by R ₁ and R ₂ include methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, octyl, 2-ethylhexyl, tertiary octyl, nonyl,
Examples include groups such as isononyl, decyl, undecyl, isodecyl, lauryl, tridecyl, isotridecyl, C10-12 mixed alkyl, tetradecyl and stearyl.

Examples of the aryl group represented by R ₁ and R ₂ include phenyl, phenylphenyl, tolyl, xylyl, ethylphenyl, butylphenyl, tert-butylphenyl, octylphenyl, isooctylphenyl, nonylphenyl and dinonyl. Phenyl, cyclohexylphenyl, 2,4-ditertiary butylphenyl, 2,4-ditertiary octylphenyl, 2,4-ditertiary amylphenyl, 2-
Groups such as tert-butyl-4-methylphenyl, 2,4,6-tri-tert-butylphenyl, 2,6-di-tert-butyl-4-methylphenyl and the like can be mentioned.

Therefore, specific examples of the pentaerythritol diphosphate compound represented by the above general formula (I) include, for example, dilauryl pentaerythritol diphosphate, di (isotridecyl) pentaerythritol diphosphate, ditetradecyl pentaerythritol diphosphate. Phosphate, distearyl pentaerythritol diphosphate, diphenyl pentaerythritol diphosphate, di (nonylphenyl) pentaerythritol diphosphate, bis (2,6-di-tert-butylphenyl)
Pentaerythritol diphosphate, bis (2,6-
Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, bis (2,6-di-tert-butyl-4)
-Ethylphenyl) pentaerythritol diphosphate, bis (2,6-ditertiary butyl-4-tertiary octylphenyl) pentaerythritol diphosphate, bis (2,6-ditertiary butyl-4-tertiary nonylphenyl) Pentaerythritol diphosphate, bis (2,4,6
-Tri-tert-butylphenyl) pentaerythritol diphosphate and the like.

The component (b) is added in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the above addition amount is 0.
If it is less than 01 parts by weight, long-term weather resistance is not exhibited.

The anti-fogging agent which is the component (c) used in the present invention is added for the purpose of imparting anti-fogging property (drip-proof property) to the vinyl chloride resin, and is usually used for agricultural coating agents. What is used as an antifogging (dripproof) imparting agent can be used. For example, sorbitan monostearate, sorbitan distearate, sorbitan sesquistearate, sorbitan monopalmitate, and sorbitan higher fatty acid ester compounds such as ethylene oxide and / or propylene oxide adducts, sorbitol fatty acid ester compounds, glycerin Examples thereof include fatty acid ester compounds. These antifogging agents can be used alone or as a mixture of two or more kinds.

The amount of component (c) added is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of the vinyl chloride resin.

The composition of the present invention also contains Li, K, Na and M.
metal salts such as g, Sr, Ca, Ba, Zn, Cd, Sn, Pb, organic Sn,
For example, the combined use of a carboxylate, a salt of an organic phosphoric acid, a phenolate, a mercaptide, etc. significantly improves the stabilizing effect of the composition.

Examples of the carboxylic acid constituting the above-mentioned carboxylic acid salt include acetic acid, propionic acid, butyric acid, valeric acid,
Caproic acid, enanthic acid, caprylic acid, neodecanoic acid,
2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid,
12-hydroxystearic acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid Acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cuminic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p- Monovalent carboxylic acids such as tertiary octyl salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, Itaconic acid, aconitic acid, thiodipropionic acid, lid Acids, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid and other divalent carboxylic acids or their monoesters or monoamide compounds, butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, melophanoic acid, pyro Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids such as mellitic acid.

As the organic phosphoric acid constituting the salt of the organic phosphoric acid, mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di (nonylphenyl) phosphoric acid, nonylphenyl phosphonate Examples thereof include esters and phosphonic acid stearyl esters.

As the phenols constituting the above phenolate, phenol, cresol, xylenol, methylpropylphenol, methyl tert-octylphenol, ethylphenol, isopropylphenol, tert-butylphenol, n-butylphenol, diisobutylphenol, isoamylphenol, dia. Millphenol, isohexylphenol, octylphenol,
Isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol, dodecylphenol, octadecylphenol,
Examples thereof include cyclohexylphenol and phenylphenol.

The amount of these metal salts added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

By using the composition of the present invention in combination with an organic phosphite compound and / or an epoxy compound, the composition exhibits an excellent synergistic effect.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono, di mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl Trithiophosphite,
Bis (neopentyl glycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, tetra (C12-15)
Mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidene bis (2 -Tert-butyl-5-methylphenol)], 1,6-hexanediol diphosphite, tetratridecyl-4,
4'-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl).
1,1,3-tris (2-methyl-5-tert-butyl-4)
-Hydroxyphenyl) butane triphosphite and the like.

The amount of the organic phosphite compound added is
0.01-5 with respect to 100 parts by weight of vinyl chloride resin
It is preferable that the amount is, especially 0.1 to 3 parts by weight.

The above-mentioned epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil,
Epoxidized tall oil fatty acid ester, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, -2-ethylhexyl or -stearyl, tris (epoxypropyl) ) Isocyanurate, 3- (2-xenoxy) -1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-
Examples thereof include epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate.

The amount of the epoxy compound added is preferably 0.01 to 20 parts by weight, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Further, the composition of the present invention prevents vaporization of water vapor to wet the surface of the crop and cause a disease in a tunnel or a house when the temperature suddenly changes between morning and evening. Therefore, an antifog agent can be added for the purpose of suppressing the generation of fog. As the anti-fog agent, all those conventionally proposed as an anti-fog agent for agricultural coating agents can be used. For example, perfluoroalkyl groups, perfluoroalkoxy groups, polyfluoroalkyl groups, perfluoroalkenyl groups can be used. A fluorine-based compound or a silane-based compound having a group, a polyfluoroalkenyl group, a perfluoroalkylene group, or the like is preferable.

Further, the composition of the present invention includes pentaerythritol, dipentaerythritol, sorbitol, mannitol, pentaerythritol or stearic acid half ester of dipentaerythritol, bis (dipentaetasthritol) adipate, glycerin, tris ( 2-hydroxyethyl) isocyanurate and other polyhydric alcohol compounds, β-diketone compounds such as dehydroacetic acid, dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, ester-containing β-diketone compounds and zinc, calcium of these β-diketone compounds, A stabilizing aid such as a metal salt such as barium can be used in combination, and thereby the stability can be further improved.

In the composition of the present invention, other inorganic compounds such as synthetic talcites, calcium phosphate, magnesium phosphate and the like can be appropriately used in combination according to the application.

If an ultraviolet absorber or a light stabilizer is added to the composition of the present invention, the light stability can be improved. Therefore, these are appropriately selected and used in combination in the composition of the present invention depending on the purpose of use. It is possible to Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, and substituted acrylonitrile-based ultraviolet absorbers, and the light stabilizers include 2,2,6,6.
-A hindered amine light stabilizer represented by a tetramethylpiperidine compound and the like.

In addition, if necessary, the composition of the present invention includes, for example, a cross-linking agent, a filler, a pigment, a foaming agent, an antistatic agent, an antifogging agent, an antiplateout agent, a surface treatment agent, a lubricant, and a flame retardant. , A fluorescent agent, an antifungal agent, a bactericidal agent, a photodegradation agent, a processing aid, a release agent, and an antioxidant can be used in combination.

[0039]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Example 1 A film having a thickness of 0.1 mm was prepared with a kneading roll using the compound shown in the following [Formulation], and the film was subjected to a weather resistance test by outdoor exposure, a residual elongation and a press sheet having a thickness of 1 mm. The state of formation of seedlings after 1 year was tested. The results are shown in [Table 1] below.

In the weather resistance test, the surface condition of the film was observed after 10 months and 20 months of outdoor exposure, and the evaluation criteria are shown in 10 levels, 1 being almost no discoloration,
10 shows that it is in a state of black browning. 1 (colorless) ────────── (black brown) 10

The residual elongation rate is indicated by the residual rate (%) in comparison with the elongation before exposure of the film after one year of outdoor exposure.

[Composition] Parts by Weight Vinyl Chloride Resin (Polymerization Degree 1300) 100 Di-2-ethylhexyl phthalate 50 Tricresyl Phosphate 5 Bisphenol A Diglycidyl Ether 2 Ba / Zn Complex Stabilizer 1.5 Zinc Stearate 0 .6 Tris (mono and di mixed nonylphenyl) phosphite 0.8 Ethylenebisstearic acid amide 0.5 Sorbitan monopalmitate 1.5 Sample compound (shown in [Table 1] below) 0.8

[0044]

[Table 1]

Example 2 The same test as in Example 1 was carried out using the formulation shown below. The results are shown in [Table 2] below.

[Blending] Parts by Weight Vinyl Chloride Resin (Polymerization Degree 1450) 100 Dioctyl Phthalate 45 Tricresyl Phosphate 5 Epoxidized Flaxseed Oil Fatty Acid Octyl 3 Ba / Zn System Liquid Complex Stabilizer 1.6 Ba / Zn System Powder Complex Stable Agent 1.0 Tetra (C12-15 mixed alkyl) bisphenol A 0.75 Diphosphite Methylenebisstearic acid amide 0.3 Polyoxyethylene sorbitan monostearate 1.2 Tetrakis (2,2,6, -tetramethyl-4- 0.25 piperidini) 1,2,3,4-tetracarboxylate sample compound (shown in [Table 2] below) 0.3

[0047]

[Table 2]

From the results of the above [Table 1] and [Table 2],
The vinyl chloride resin composition of the present invention containing the pentaerythritol diphosphate compound represented by the general formula (I) retains weather resistance for a long period of time, and
It can be seen that the residual elongation is also excellent, and no spots occur on the resin sheet.

On the other hand, a vinyl chloride resin composition which does not use the pentaerythritol diphosphate compound represented by the general formula (I) according to the present invention or a vinyl chloride which uses a conventional organic phosphite compound. The resin composition shows a certain degree of weather resistance up to about 10 months, but after a long period of 20 months, it volatilizes and the weather resistance remarkably deteriorates. Moreover, the residual elongation rate decreases and the resin sheet becomes You can see that things are coming out.

[0050]

The agricultural vinyl chloride composition of the present invention comprises:
By adding a specific pentaerythritol diphosphate compound to a vinyl chloride resin in combination with a plasticizer and an antifogging agent, it has excellent long-term weather resistance. Therefore, the agricultural vinyl chloride composition of the present invention has been practically improved by being used in an agricultural house or tunnel that can be used for extension for a long period of time.

Claims (1)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
(A) 20 to 90 parts by weight of a plasticizer, (b) 0.01 to 10 parts by weight of a pentaerythritol diphosphate compound represented by the following general formula (I), and (c) an antifogging agent of 0.1. A vinyl chloride resin composition for agriculture, comprising 1 to 5 parts by weight. [Chemical 1]