JPH05295207A - Agricultural vinyl chloride-based resin film - Google Patents

Abstract

PURPOSE:To obtain the subject film excellent in the resistance to deterioration in the soil without impairing the characteristics as a covering material by blending a vinyl chloride-based resin with a specific phthalic ester plasticizer and epoxy resin. CONSTITUTION:The objective agricultural film can be obtained by incorporating (A) 100 pts.wt. of a vinyl chloride-based resin blending with (B) 40-60 pts.wt. of a phthalic ester plasticizer containing >=5wt.% of a m-phthalic ester plasticizer (e.g. m-dihexyl phthalate, m-octylnonyl phthalate) and, optionally, another plasticizer, and (C) 0.5-5 pts.wt. of an epoxy resin (e.g. bisphenol A diglycidyl ether, dicyclopentadiepoxide), and, as necessary, (D) each <=5 pts.wt. of other ingredient (s) (e.g. thermal stabilizer, ultraviolet light absorber, light stabilizer, lubricant, filler). This film is pref. provided, at least on one side, with a coating film derived from a solvent-type, water-based type or ultraviolet-curing type coating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent resistance to deterioration in soil,
The present invention relates to an agricultural vinyl chloride resin film having extremely high usefulness, which achieves these important properties economically and inexpensively without deteriorating other properties required as a covering material.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin films, polyethylene films, ethylene-vinyl acetate copolymer films, coating materials for houses and tunnels,
Polyester film is used. Among them, the soft vinyl chloride resin film is evaluated as having a good balance of various characteristics such as light transmittance, heat retention, mechanical strength, durability, workability, and economical efficiency. Since it is the best, it is widely used, accounting for about 90% of agricultural covering materials. When used as a covering material for houses and tunnels, the framework of the house is made of steel, etc., these frameworks are covered with vinyl chloride resin film for agriculture, and the end of the vinyl chloride resin film for agriculture is used in the lower part of the house and tunnel. The part was fixed by burying it in the soil. However, especially in the case of greenhouses and tunnels using vinyl chloride resin film for agriculture, the part buried in the soil deteriorates faster than the part exposed to the outside, and the part exposed to the outside has no problem. However, there was a problem that the soil part deteriorated and it was necessary to replace it early.

In recent years, since greenhouses have been used for year-round cultivation and it takes time and labor to replace the film, it is more likely that the film will be used for the next year without replacement, and the resistance to deterioration in soil will increase. It is becoming more and more demanding.

[0004]

Under the circumstances, the present inventor has surprisingly studied as a result of an earnest study for the purpose of providing an agricultural vinyl chloride resin film having excellent resistance to deterioration in soil. By using an m-phthalate ester plasticizer as a plasticizer together with an epoxy resin, a vinyl chloride resin for agriculture which is extremely excellent in soil resistance without deteriorating other properties required as a coating material. The inventors have found that a film can be obtained and completed the present invention.

[0005]

That is, the agricultural vinyl chloride resin film of the present invention comprises a vinyl chloride resin 10
A vinyl chloride resin film comprising 40 to 60 parts by weight of a phthalate ester plasticizer and 0.5 to 5 parts by weight of an epoxy resin per 0 parts by weight, wherein the phthalate ester plasticizer is m. -Containing 5% by weight or more of phthalate ester.

As the vinyl chloride resin used in the present invention, in addition to polyvinyl chloride, vinyl chloride and other vinyl monomers such as vinylidene chloride, acrylonitrile, maleic acid, itaconic acid, methacrylic acid, vinyl acetate, ethylene, propylene. , A maleic acid ester, a methyl methacrylate, a methacrylic acid ester, an acrylic acid ester, a copolymer with a higher vinyl ether, or a blend thereof.

As the plasticizer, one containing at least 5% by weight of the total amount of the m-phthalate ester plasticizer must be used. The m-phthalate ester is
Those represented by the following general formula can be used. (R ₁ and R ₂ are linear or branched alkyl groups, and R ₁ and R ₂ may be the same, different, or any of them.) Specifically, m-dihexyl phthalate, m-diheptyl phthalate, m-dioctyl phthalate, m-
Dinonyl phthalate, m-didecyl phthalate, m-diundecyl phthalate, m-didodecyl phthalate, m
-Octyl nonyl phthalate, m-octyl decyl phthalate, m-octyl undecyl phthalate, m-octyl dodecyl phthalate, m-nonyl decyl phthalate, m-nonyl undecyl phthalate, m-nonyl dodecyl phthalate, m-hexyl heptyl phthalate, m
-Hexyl octyl phthalate, m-hexyl nonyl phthalate, m-hexyl decyl phthalate, m-hexyl undecyl phthalate, m-heptyl octyl phthalate, m-heptyl nonyl phthalate, m-heptyl decyl phthalate, m-heptyl undecyl phthalate,
Examples thereof include m-heptyl dodecyl phthalate, m-decyl undecyl phthalate, and m-decyl dodecyl phthalate. These m-phthalic acid ester plasticizers can be used alone or in combination of two or more.

The phthalate ester plasticizer used in combination with the m-phthalate ester plasticizer includes o-dihexyl phthalate, o-heptyl phthalate, o-dioctyl phthalate, o-dinonyl phthalate, o-didecyl phthalate, o-diundecyl phthalate, o-didodecyl phthalate, o-octyl hexyl phthalate, o-octyl heptyl phthalate, o-octyl nonyl phthalate, o-octyl decyl phthalate, o-octyl undecyl phthalate, o-octyl dodecyl phthalate, o -Nonyldecyl phthalate, o-nonyl undecyl phthalate, o-nonyl dodecyl phthalate, o-pentyl nonyl phthalate, o-pentyl decyl phthalate, o-pentyl undecyl phthalate, o-butyl benzyl phthalate, - octyl capryl phthalate,
Examples thereof include o-ethylphthalylethyl glycolate, o-methylphthalylethyl glycolate, and o-butylphthalylethyl glycolate. These phthalate ester plasticizers can be used alone or in combination of two or more. ..

The mixing ratio of the vinyl chloride resin and the phthalic acid ester plasticizer is appropriately selected depending on the kind of the phthalic acid ester plasticizer, the kind of the synthetic resin, the mixing ratio of the synthetic resin, the use of the film and the like. The optimum ratio is 40% by weight of the plasticizer per 100 parts by weight of the vinyl chloride resin.
It is 60 parts by weight. 5% by weight or more of this plasticizer amount is m-
Must be a phthalate plasticizer. When the content of the m-phthalate ester plasticizer is less than 5% by weight of the total plasticizer, the soil deterioration resistance cannot be sufficiently improved. Of course, the total amount of the plasticizer may be the m-phthalate ester plasticizer.

As a plasticizer other than the phthalate ester plasticizer, a fatty acid ester plasticizer, a phosphate ester plasticizer, a trimellitic acid ester plasticizer, an epoxidized oil plasticizer, a polyester plasticizer, etc. are used in combination. You can do it.

Examples of the fatty acid ester plasticizer include dioctyl adipate, dioctyl azelate, dioctyl sebacate, triacetyl glycerin, glycerol sebacate, diisodecyl succinate, diisodecyl adipate, and succinic acid mixed alkyl ester.

Examples of the phosphoric acid ester type plasticizers include tributyl phosphate, tricresyl phosphate, trixylenyl phosphate, triphenyl phosphate, trichloroethyl phosphate, trioctyl phosphate, triethyl phosphate, triethylphenyl phosphate, diphenylcresyl phosphate and mono. Examples thereof include phenyl dicresyl phosphate, dicresyl monoxylenyl phosphate, monocresyl dixylenyl phosphate, diphenyl monoxylenyl phosphate, monophenyl dixylenyl phosphate, and tris (isopropylphenyl) phosphate.

As a trimellitic acid ester plasticizer. Examples include trimellitic acid trioctyl ester, epoxidized oil-based plasticizers such as epoxidized soybean oil and epoxidized linseed oil, and polyester-based plasticizers such as adipic acid-based polyester and sebacic acid-based polyester. Is mentioned.

The epoxy resin added to the vinyl chloride resin together with the phthalate ester plasticizer includes 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, vinylcyclohexene diepoxide, dicyclopentadiepoxide, bisphenol A.
-Diglycidyl ether, 3- (2-xenoxy) -1,2-epoxypropane, a condensate of 2,2-bis (4-hydroxyphenyl) propane and epihalohydrin, etc. can be used.
These epoxy resins can be used alone or in combination of two or more kinds. The amount of the epoxy resin added is 0.5 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. It is not sufficient, and even if the amount of the epoxy resin added exceeds 5 parts by weight, the deterioration resistance in soil is not promoted.

The vinyl chloride resin film of the present invention comprises:
As additives other than the above, heat stabilizers, lubricants or antiblocking agents, ultraviolet absorbers, antioxidants, light stabilizers, fillers, colorants, antifungal agents, algae inhibitors, organophosphate metal salts, etc. In general, additives that can be added to plastics can be included.
It is preferable to use each of these additives in an amount of 5 parts by weight or less based on 100 parts by weight of the vinyl chloride resin.

As the heat stabilizer, commonly used stabilizers such as metal soap and organic phosphite stabilizer can be used.
Examples of the metal soap include zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate, calcium oleate, zinc octoinate, etc. Examples thereof include phosphite, tris (nonylphenyl) phosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, tristearylphosphite, and octyldiphenylphosphite. Further, tin-based stabilizers such as dibutyltin dilaurate, dibutyltin malate, organic tin mercaptide, and organic tin sulfonamide can be used. These stabilizers alone or
It can be used in combination of two or more species.

As the lubricant or anti-tacking agent, fatty acid lubricants such as stearic acid, isostearic acid, palmitic acid and myristic acid, stearic acid amide, palmitic acid amide, methylene bis stearoamide, ethylene bis stearoamide, ethylene bis. Examples thereof include saturated fatty acid amide-based lubricants such as oleylamide and ethylenebislaurylamide, ester-based lubricants such as butyl palmitate and butyl stearate, polyethylene wax, liquid paraffin, etc. One or more of these may be used. it can.

As the ultraviolet absorber, 2-hydroxy-4-
Methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybezophenone, 2-
Hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxybenzoyloxybezophenone, 2,2'-dihydroxy-4-methoxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, bis- (2-methoxy-
4-hydroxy-5-benzoylphenyl) benzophenone-based UV absorbers such as methane, 2- (2'-hydroxyphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2'- Hydroxy-5'-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfonebenzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5 ' -Aminophenyl) benzotriazole, 2- (2'-hydroxy-3 ',
5'-dimethylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) -5-methoxybenzotriazole, 2- (2'-methyl-4'-hydroxyphenyl) benzotriazole, 2- (2'-stearyloxy-3 ', 5'-dimethylphenyl) -5-methylbenzotriazole, 2- (2'-
Hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-hydroxy-3'-methyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-cyclohexylphenyl) benzotriazole, 2- (2'-hydroxy-4 ', 5'-dimethylphenyl) -5-carboxylic acid benzotriazole Butyl ester, 2- (2'-hydroxy-3 ', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-4', 5'-dichlorophenyl) benzotriazole, 2- (2 ' -Hydroxy-3 ', 5'-dimethylphenyl) -5-ethylsulfone benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methoxy Phenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid ester benzotriazole, 2-
In addition to benzotriazole-based UV absorbers such as (2'-acetoxy-5'-methylphenyl) benzotriazole, salicylic acid ester-based UV absorbers, cyanoacrylate-based UV absorbers, and the like, and one or two of these may be mentioned. The above can be used.

As the antioxidant, one or more antioxidants such as phenol type, thiodipropionate type and aliphatic sulfide type can be used.

As the light stabilizer, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, tris- (2,2,6,
6, -Tetramethyl-4-piperidyl) triazine-2,4,
One or more commonly used light stabilizers such as hindered amines represented by the following general formula such as 6-tricarboxylate can be used. General formula (In the formula, R represents a mono-to tetra-arsyl group derived from a mono- to tetra-valent carboxylic acid, R _{1 to} R ₄ represent an alkyl group having 1 to ₄ carbon atoms, and n represents an integer of 1 to 4.)

The filler can be used for the purpose of preventing stickiness of the film surface and improving heat retention. As such a filler, any one can be used as long as it is an inorganic and / or organic filler excellent in heat resistance that does not cause physical or chemical changes such as melting or decomposition at the processing temperature. , The following is an example. Inorganic fillers such as magnesium carbonate, magnesium silicate, silicon oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, talc, hydrotalcite, etc., as well as crosslinked vinyl chloride resin powder, acrylic resin powder, etc. Organic fillers such as crosslinked thermoplastic resin powders can be used, and these may be used alone or in combination of two or more. The particle size of the filler is preferably 20 μm or less. The addition amount of this filler is 1
The range of 1 to 20 parts by weight is preferable with respect to 00 parts by weight.

As the coloring material, carbon black, ultramarine blue, phthalocyanine blue, phthalocyanine green,
Commonly used pigments and dyes such as titanium oxide, zinc oxide, quinacridone red, and Hansa yellow can be used, and these can be used alone or in combination of two or more kinds.

Antifungal agents and algae inhibitors include tributyltin laurate, 2- (4-thiazolyl) benzimidazole,
2,4,5,6-Tetrachloroisophthalonitrile, paraoxybenzoic acid ester, 5-bromo-5-nitro-1,3-dioxane, 3-methyl-4-chlorophenol, 2,3,5,6- Tetrachloro-4-methylsulfonylpyridine, N- (tetrachloroethylthio) phthalimide, 10,10'-oxybisphenoxyarsine, N- (fluorodichloromethylthio) phthalimide, N-dimethyl-N'-phenyl- (N'-fluoro Dichloromethylthio) sulfamide and the like can be used, and these can be used alone or in combination of two or more kinds.

As the organic phosphoric acid metal salt, those represented by the following general formula can be used. (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are any of an alkyl group, an allyl group, and an alkylallyl group, and M is a divalent metal such as zinc, calcium, magnesium, or barium. )

At least one side of the vinyl chloride resin film for agriculture of the present invention can be provided with a film made of a solvent type, an aqueous type, or an ultraviolet curing type paint. Deterioration is improved, which is preferable. Examples of solvent-based, water-based, or UV-curable coating materials include the following. As the solvent type, various acrylic resins, cellulose resins and the like dissolved in a solvent can be used. The resin dissolved in the solvent may be a single resin, or may be a mixture of a plurality of types of resins dissolved. What melt | dissolved acrylic resin is preferable in terms of performance.
It is particularly preferable that the coating film is partially crosslinked by adding a crosslinking agent. An acrylic resin emulsion or the like can be used as the water-based type. As the ultraviolet curing type, acrylic type, acrylic modified urethane type, acrylic modified epoxy type, mercapto derivative type, epoxy resin type and the like can be used.

[0026]

According to the present invention, a vinyl chloride resin film comprising 40 to 60 parts by weight of a phthalate ester plasticizer and 0.5 to 5 parts by weight of an epoxy resin per 100 parts by weight of a vinyl chloride resin. Since the phthalate ester-based plasticizer contains m-phthalate ester in an amount of 5% by weight or more, the phthalate ester plasticizer has excellent resistance to deterioration in soil and has no effect on other properties required for agricultural coating materials. Not give
It is extremely useful. Further, when a coating derived from a solvent-based, water-based or UV-curable coating is formed on at least one surface, it is further excellent in soil deterioration resistance and can be used for a long period of time.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The evaluation of soil deterioration was performed according to the following criteria. << Deterioration Resistance in Soil >> The deterioration resistance in soil was judged based on the residual elongation value of the film. The film is attached to the side part of the house, the lower part of the house is buried in the soil, the film after one year has passed is collected, washed with water and dried at room temperature,
The elongation (L ₁ ) of the sampled film is measured by JIS K-6732, the elongation (L ₂ ) of the unused film is measured, and the residual elongation rate is calculated by the following formula. Residual elongation rate (%) = (L ₁ / L ₂ ) × 100 The larger the value of the residual elongation rate, the better the soil deterioration resistance.

Example 1 100 parts by weight of vinyl chloride resin, 45 parts by weight of o-dioctyl phthalate, 5 parts by weight of m-dioctyl phthalate, 3 parts by weight of tricresyl phosphate, 2 parts by weight of epoxy resin (Epicoat 828), Ba-Zn A vinyl chloride resin film having a thickness of 0.1 mm was prepared at 180 ° C. on a roll by using a mixture of 2.5 parts by weight of a system stabilizer and 0.3 parts by weight of ethylenebisstearoamide. As a result of testing the film according to the above-described evaluation method of soil deterioration, the residual elongation of this film was 77%.

Example 2 A vinyl chloride resin film was prepared in the same manner as in Example 1 except that o-octylnonyl phthalate was used instead of o-dioctyl phthalate. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 75%.
Met.

Example 3 A vinyl chloride resin was prepared in the same manner as in Example 1 except that 50 parts by weight of m-dioctyl phthalate was used instead of the mixed plasticizer of 45 parts by weight of o-dioctyl phthalate and 5 parts by weight of m-dioctyl phthalate. A film was prepared. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 82%.

Example 4 The same procedure as in Example 1 was repeated except that 5 parts by weight of m-dinonyl phthalate was used instead of 5 parts by weight of m-dioctyl phthalate, and trixylyl phosphate was used instead of tricresyl phosphate. A vinyl chloride resin film was prepared. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 77%.

Example 5 A vinyl chloride resin film was prepared in the same manner as in Example 1 except that 10 parts by weight of m-octylnonyl phthalate was used instead of 5 parts by weight of m-dioctyl phthalate.
The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 79%.

Example 6 A vinyl chloride resin film was prepared in the same manner as in Example 1 except that 15 parts by weight of m-diundecyl phthalate was used instead of 5 parts by weight of m-dioctyl phthalate. The obtained film was tested in the same manner as in Example 1,
The residual elongation rate was 78%.

Example 7 A vinyl chloride resin film was prepared in the same manner as in Example 1 except that 10 parts by weight of m-hexyldecyl phthalate was used instead of 5 parts by weight of m-dioctyl phthalate. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 80%.

Example 8 A mixture of 45 parts by weight of o-dioctyl phthalate and 5 parts by weight of m-dioctyl phthalate was replaced with 40 parts by weight of m-dioctyl phthalate and 10 parts by weight of m-diundecyl phthalate. A vinyl chloride resin film was prepared in the same manner as in Example 1. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 85%.
Met.

Comparative Example 1 Vinyl chloride resin was prepared in the same manner as in Example 1 except that 50 parts by weight of o-dioctyl phthalate was used in place of the mixed plasticizer of 45 parts by weight of o-dioctyl phthalate and 5 parts by weight of m-dioctyl phthalate. A film was prepared. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 62%.

Comparative Example 2 Instead of the mixed plasticizer of 45 parts by weight of o-dioctyl phthalate and 5 parts by weight of m-dioctyl phthalate, a mixed plasticizer of 48 parts by weight of o-dioctyl phthalate and 2 parts by weight of m-dioctyl phthalate was used. Example 1 except that
A vinyl chloride resin film was prepared in the same manner as in. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 66%.

Comparative Example 3 Vinyl chloride resin film was prepared in the same manner as in Example 1 except that o-dinonyl phthalate was used in place of the mixed plasticizer of 45 parts by weight of o-dioctyl phthalate and 5 parts by weight of m-dioctyl phthalate. Was prepared. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 65.
%Met.

Comparative Example 4 A vinyl chloride resin film was prepared in the same manner as in Example 1 except that the epoxy resin was not used. The obtained film was tested in the same manner as in Example 1, and as a result, the elongation residual ratio was 63.
%Met.

From Examples 1 to 8, the agricultural film of the present invention has excellent resistance to deterioration in soil, and does not require replacement due to deterioration even when used for a long period of time. On the other hand, Comparative Example 2 in which the content of the m-phthalate ester plasticizer in the plasticizer was less than 5% by weight of all the phthalate ester plasticizers, and the m-phthalate ester plasticizer was used at all. Comparative Examples 1 and 3 which are not used, and Comparative Example 4 which does not use an epoxy resin are inferior in deterioration resistance in soil, cannot be used for a long period of time, and must be replaced in a short period of time. From these Examples and Comparative Examples, an agricultural film having excellent resistance to deterioration in soil can be obtained due to the interaction of 5% by weight or more of the phthalic acid ester plasticizer with the m-phthalic acid ester plasticizer and the epoxy resin. I understand.

[0041]

Industrial Applicability As described above, the agricultural vinyl chloride resin film of the present invention contains 40 to 60 parts by weight of a phthalate ester plasticizer per 100 parts by weight of vinyl chloride resin.
A vinyl chloride resin film containing 0.5 to 5 parts by weight of an epoxy resin, wherein the phthalate ester plasticizer contains 5% by weight or more of m-phthalate ester. It is excellent in deterioration. Therefore, when the agricultural vinyl chloride resin film of the present invention is used in a house, the solar radiation is well transmitted for a long period of time, and the film embedded in the soil does not deteriorate in a short period of time, and the It can be placed in a stretched state without re-covering and is easy to manage the house, which is extremely useful for crop cultivation.

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Claims (1)

[Claims] 1. A vinyl chloride resin film comprising 40 to 60 parts by weight of a phthalate ester plasticizer and 0.5 to 5 parts by weight of an epoxy resin per 100 parts by weight of a vinyl chloride resin. Phthalates plasticizer is m-
A vinyl chloride resin film for agriculture, which contains 5% by weight or more of a phthalate ester.