JPS6137834A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PURPOSE:The titled film excellent in weather resistance and dustproofness but yet inexpensive, containing two phthalate plasticizers and an organic phosphate. CONSTITUTION:100pts.wt. vinyl chloride resin is mixed with (A) a phthalate plasticizer of formula I (wherein R1 and R2 are each a 2-18C alkyl), e.g., diethyl phthalate, (B) a phthalate plasticizer of formula II (wherein R3 is a 2-18C alkyl, R4 is aryl or cycloalkyl), e.g., ethyl benzyl phthalate, and (C) an organic phosphate (e.g., trixylenyl phosphate). The total of the amounts of the components (A)-(C) is 40-60pts.wt. provided that the amount of component C is about 1-10pts.wt. and the ratio B/C is 1:2-20:1 (by weight).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a vinyl chloride resin film for agricultural use. More specifically, the present invention relates to an agricultural vinyl chloride resin film that has excellent weather resistance and dust resistance.

``Conventional technology'' In recent years, with the modernization of agriculture, greenhouse cultivation of useful plants has become booming, and glass, polyethylene film, and polyvinyl chloride are used as cover materials for greenhouse cultivation. films, ethylene-vinyl acetate copolymer films, etc. have been used. Among them, polyvinyl chloride film has excellent heat retention, transparency, strength, workability, etc., and is relatively inexpensive, so it is currently the mainstream material for bunkers.

However, when a general polyvinyl chloride film is used outdoors, it browns and deteriorates within several months. In polyvinyl chloride film used as an agricultural material, various additives are added to the resin raw material before film formation in order to eliminate the drawback of browning and deterioration when used outdoors. For example, various stabilizers against light, heat, and oxidation, such as organotin stabilizers, metal soap stabilizers, lead stabilizers, organic cadmium stabilizers, organic barium stabilizers, antioxidants, and ultraviolet absorbers. is blended.

However, among these, it is rare to find one that exhibits a remarkable stabilizing effect even when added in small amounts. Of course, adding a large amount may improve weather resistance, but on the other hand, it usually leads to a decrease in physical properties such as processability and transparency.

For example, if a large amount of metal soap stabilizer is added.

Plate-out occurs during the film forming process, impairing the appearance and transparency of the product film, and significantly reducing the efficiency of the film forming process. For example, if a large amount of ultraviolet absorber is added, the product film will be colored yellow, and when used as an agricultural cover, 300-≠0 of the sun's rays will be used.
Light in the 0 millimicron range is absorbed by the film, which may inhibit the growth of some plants. For these reasons, not much can be expected from the method of blending a large amount of stabilizer into a resin raw material to form a film.

Recently, a method has been proposed in which tricresyl phosphate and tricylenyl phosphate are added to improve the weather resistance of vinyl chloride resin films used as agricultural cover (Tokukosho, ? (See Japanese Patent Publication No. J-7316, Japanese Patent Publication No. 3O-3JJμ2, etc.). Films containing these compounds have significantly improved weather resistance, but bleed-out (a phenomenon in which liquid additives are spewed out onto the film surface) occurs on the film surface, and the bleed-out liquid is contaminated with dust. There was a problem in that dust-proof properties were significantly reduced due to the adhesion of dust.

In order to solve the above bleed-out problem, there is a method of reducing the amount of plasticizer added to the resin raw material, but this method reduces the flexibility of the film itself, so when the film is used outdoors. Tears are more likely to occur. Another method to eliminate bleed-out is to form an acrylic resin coating on the film surface (for example, see Japanese Patent Publication No. 4/93), but it has been put into practical use because it is effective. However, it cannot be denied that the cost will be high.

[Problems to be Solved by the Invention] Under such circumstances, the present inventors set out to provide an agricultural vinyl chloride resin film that has excellent weather resistance and dust resistance, and does not increase costs. As a result of intensive study, we finally completed the F18J.

"Means for Solving the Problems" The gist of the present invention is to add (A) a phthalate ester plasticizer represented by the general formula (1) to a vinyl chloride resin, (B) a general formula (1). A phthalate ester plasticizer represented by (II) [In formula (■) and formula (U), each of R1s R2 and R3 is a group selected from linear or branched alkyl groups of at to ○I3 , R4 represents a group selected from an aryl group or a cycloalkyl group. ] (0) The three components of the organic phosphate ester are blended within the range of The present invention relates to an agricultural vinyl chloride resin film characterized in that the ratio is within the range of 20 to 20 pairs.

The present invention will be explained in detail below.

In the present invention, the vinyl chloride-based resin refers to a flavor containing not only polyvinyl chloride but also a copolymer whose main component is vinyl chloride. Monomers that can be copolymerized with vinyl chloride include vinylitine chloride, ethylene, furopyrene, acrylonitrile, vinyl acetate, maleic acid, itaconic acid, acrylic acid, acrylic esters, methacrylic acid,
Examples include methacrylic acid esters.

The vinyl chloride resin may be used alone or in a mixture of two or more.

Vinyl chloride resins can be produced using suspension polymerization, emulsion polymerization, and emulsion polymerization.
It may be manufactured by any of the conventionally known manufacturing methods such as suspension polymerization, solution polymerization, and bulk polymerization. The degree of polymerization of vinyl chloride resin is zaoo, 2soo
You can choose from a range of

The vinyl chloride resin film according to the present invention includes the above-mentioned vinyl chloride-based resin, a phthalate ester plasticizer represented by the above formula (1) as the (A) component, and the above (n) as the (B) component. A phthalate ester plasticizer represented by the formula is blended.

According to experiments conducted by the present inventor, if a large amount of only the plasticizer represented by the formula (I) is used as a plasticizer in a vinyl chloride resin, bleed-out may occur during use after forming into a film. It has been found that if only a large amount of the plasticizer represented by formula (II) is used, the weather resistance of the film will be poor. In order to eliminate both drawbacks, a plasticizer represented by the formula (■) and (If
It has been found that it is best to use the plasticizer represented by the formula:

Examples of the phthalate ester-based plasticizers represented by the formula (1) include diethyl phthalate, diisopropyl phthalate, di-n-butyl heptatalate, diisobutyl heptatalate, di-S-butyl phthalate, and di-t-butyl. Phthalate, diethyl phthalate, diypentyl phthalate, di-t-pentyl phthalate, diisononyl phthalate, diisohexyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, diisononyl phthalate, dilauryl phthalate, dioctyl phthalate, etc. . Component (A) represented by formula (I) may be used alone or in combination of two or more.

Examples of the phthalate ester plasticizers represented by the formula (It) include ethyl cresyl phthalate, ethyl phenyl phthalate, ethyl cresyl phthalate, ethyl xylenyl phthalate, butyl benzyl phthalate, butyl phenyl phthalate, butyl cresyl heptatalate, butyl Xylenyl phthalate, butylcyclohexyl phthalate-
8-late, octylbenzyl phthalate, octylphenyl phthalate, octyl cresyl phthalate, octyl xylenyl phthalate, octyl fuchlorohexyl phthalate, and the like.

Component (B) represented by formula (II) may be used alone or in combination of two or more.

The agricultural vinyl chloride resin film according to the present invention is (C
) Contains an organic phosphate ester as a component.

Examples of organic phosphate esters include tricresyl phosphate, triisopropylphenyl phosphate, tributyl phosphate, triethyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, indecyl diphenyl phosphate, tricylenyl phosphate, etc. can be given. These (0) components may be used alone or in combination of two or more. Among the above organic phosphoric acid esters, tricylenyl phosphate is preferable, and when producing tricylenyl phosphate, the ratio of the xylenol component in the raw alcohol is 50% by weight.
Products using the above alcohols are particularly desirable.

The component (A) blended into the raw material vinyl chloride resin, (
For children with component B) and component (0), the total amount is II O~A
OPHR(Per Hundred Re5in,
(parts by weight based on 100 parts by weight of resin). When the total amount is less than ≠0 PHR, bleed-out is small and the film has excellent dustproof properties, but it is not preferable because the film has poor flexibility and is easily torn.

When the total amount is greater than AOPHR, the flexibility of the film is excellent, but bleed-out increases and the dustproof properties of the film deteriorate, which is not preferable.

It is preferable that the above-mentioned three components be blended into the raw material vinyl chloride resin. If the ratio of both components is small, the film will not have the effect of improving dustproof properties, and if it is larger than 20 ratios, the weather resistance of the film will be poor, which is not preferable. .

The component (C) blended into the raw material vinyl chloride resin is /
If it is less than PHR, the film will have poor weather resistance, which is undesirable, and if it is more than /OPHR, the film will have poor dust resistance and weather resistance, so it is preferable to select it within the range of / to /OPHH.

In addition to the above three components, the agricultural vinyl chloride resin film according to the present invention contains other plasticizers not represented by the formula (I) or the formula (IT), an antifogging agent, an antistatic agent, and a purple IAme absorbent. , stabilizers, antioxidants, stabilizing aids, fungicides, algaecides, colorants, and other various resin additives.

Other plasticizers include di-n-butyl adipate, di-
n-octyl adipate, diisooctyl adipate,
Adipic acid esters such as di-2-ethylhexyl adipate, diisodecyl adipate, diinnonyl adipate, di-n-octyl azelate, diisooctyl azelate, dicoethylhexyl azelate, diisobutyl azelate, diisononyl azelate, diisodecyl azelate azelaic acid esters such as salt; aliphatic divalent carboxylic acid ester plasticizers such as sebacic acid esters such as diptyl sebacate, di-2-ethylhexyl sebacate, diisononyl sebacate, diisodecyl sebacate; epoxidized soybean oil , epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized middle fat oil, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil fatty acid ester, epoxidized polybutadiene, epoxy methyl stearate, epoxy Butyl stearate, coethylhexyl epoxy stearate, stearyl epoxy stearate, tris(epoxypropyl)in cyanurate, J-(j
-xenoxy)-l2.2-epoxypropane, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, 2-bis(μm hydroxy-
Examples include epoxidized plasticizers such as polycondensates of 12-.phenyl)propane and epichlorohydrin.

Compounds that can be used as 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, diglycerin fatty acid/dibasic ester Examples include acid esters, glycerin fatty acid/dibasic acid esters, and compounds obtained by adding alkylene oxides such as ethylene oxide, globylene oxide, butylene oxide, and the like.

Among such compounds, esters of fatty acids having 72 to 22 carbon atoms and dibasic acid esters thereof are preferred.

Specific examples of these compounds include sorbitan palmitate, sorbitan stearate, sorbitan stearate-3 mole adduct of ethylene oxide, nrubitan palmitate-2 mole adduct of propyletine oxide, nrubitol snaate, and sorbitol stearate-3 mole adduct. Ethylene oxide 3-molar adduct, diglycerin palmitate, diglycerin stearate, chrycerin stearate, glycerin palmitate/ethylene oxide-molar adduct, sorbitan stearate atubeton propylene oxide 1-molar adduct, sorbitol stearate ) 7 dipate/3 mol ethylene oxide/3 mol propylene oxide adduct, diglycerin palmitate sebacate/propylene oxide 2 mol adduct, sorbitol palmitate/adipate/propylene oxide 3 mol adduct, and the like. These specific examples do not limit the present invention. These antifogging agents can be used alone or in combination of two or more.

Examples of compounds that can be used as antistatic agents include polyoxyethylene alkylamine, poly/IJ coal ether, and sodium p-styrenesulfonate. These antistatic agents can be used alone or in combination of two or more.

Examples of compounds that can be used as ultraviolet absorbers include the following.

Benzotriazole UV absorber □J -(2'-hydroxy-3',3/-di-tert-butylphenyl)-j-chlorobenztriazole, 2-(j'-hydroxy-3'-tert-butyl-j '-methylphenyl)-yo-chlorobenztriazole, 2- (,2
'-Hydroxy-3'-tθrt=amyl-j'-isobutylphenyl)-4-chlorobenzotriazole, 2
-(2'-Hydroxy-3'-inbutyl-j'-methylphenyl)-! -chlorobenzotriazole, 2-(
2'-Hydroxy-3'-isobutyl-j'-propylphenyl)-5-chlorobenzotriazole, co(2
'-Hydroxy-3',5/-di-tert-butylphenyl)hensoto! J ”)”-ru, -2-(2'-
Hydroxy-sl)tylphenyl)penztriazole, -1[2'-hydroxy-j'-(/,/.

3.3-Tetramethylbutyl)phenyl]benzotriazole.

Benzophenone UV absorber - Tips. 2'-Dihydroxy-t-methoxybenzophenone, 2.2'-dihydroxy-≠, ≠'-dimethoxybenzo7/7,
2.2', 'l,'I'-tetrahydroxybenzophenone, λ-hydroxy-gmethoxybenzophenone, 2. Kudihydroxybenzophenone, -monohydroxy-der octoxibe/siphenon, salicylic acid-based ultraviolet absorber-phenyl salicylate, para-octylphenyl salicylate ultraviolet absorbers can be used alone or in combination of two or more. Among those exemplified above, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers are particularly preferred.

Compounds that can be used as stabilizers include dibutyltin dilaurate, dibutyltin maleate ester, dioctyltin mercaptide, calcium stearate, barium stearate.

Examples include zinc stearate, calcium laurate, barium ricinoleate, calcium oleate, zinc octoate, and the like. These stabilizers can be used alone or in combination of two or more.

Compounds that can be used as antioxidants include λ, t-
Tert-butyl-Hiro-methylphenol, λ, 2
'-methylenebis(A-tert-butyl-kuethylphenol), dilaurylthiodiglobionate, and the like. These antioxidants can be used alone or in combination of two or more.

Compounds that can be used as stabilizing aids include triphenyl phosphite, dioctyl phenyl phosphite,
Examples include tris(nonylphenyl) phosphite, diphenylisodecyl phosphite, trilauryl trithiophosphite, diphenyl acid phosphite, dioctyl acid phosphite, and the like. These stabilizing aids can be used alone or in combination of two or more.

Compounds that can be used as fungicides and algaecides include 1.
2.4t,j,J-tetrachloroisophthalonitrile,
io, io'-oxybisphenoxyarsine,
-1(kuthiazolyl)-benzimidazole, N(fluorodichloromethylthio)phthalimide, N-dimethyl-N'-phenyl-(N'~fluorodichloromethylthio)sulfamide, paraoxybenzoic acid ester, j-
Bromo-yo-nitro/, 3-dioxane, λ, 3. !
, t-tetrachloro-Hiro-methylsulfonylpyridine, 3-methyl-≠-chlorophenol, N(tetrachloroethylthio)phthalimide, tributyltin laurate, and the like. These compounds can be used alone or in combination of two or more.

Examples of colorants that can be used include phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc white, permanent red, quinacridine, and carbon black. These colorants can also be used alone or in combination of two or more.

The above various resin additives, including other plasticizers, can be selected within a range that does not deteriorate the properties of the film, usually within a range of 5 parts by weight or less based on 100 parts by weight of the base vinyl chloride resin. .

The above (A) component, (B) component, to the base vinyl chloride resin,
In order to blend the component (C) and the resin additive, the necessary amounts of each may be weighed out and a conventionally known blender or mixer such as a ribbon blender, Banbury mixer, super mixer, or the like may be used.

The resin composition thus obtained can be formed into a film by a method known per se, such as melt extrusion method (T-
Conventionally known methods such as die method, inflation method), calendar molding method, solution casting method, etc. may be used.

If the thickness of the film is too thin, the strength will be insufficient, which is undesirable.On the other hand, if the film is too thick, it will be inconvenient during the film forming process and subsequent handling (including cutting, gluing, stretching, etc.). The range is preferably from 0.03 to 0.3, preferably from o, oj to 0.2.

The agricultural vinyl chloride resin film according to the present invention can be used for covering greenhouses, tunnels, etc., and can also be used for mulching.

"Effects of the Invention" The present invention, which has been described in detail above, has the following particularly remarkable effects, and its industrial utility value is extremely high.

(1) The agricultural vinyl chloride resin film according to the present invention contains the above-described components (A), (B), and (O) in a specific range, so the film does not bleed. Since there is little outflow and the surface is not sticky, it is difficult for dust to adhere to it, and it exhibits excellent dust resistance.

(2) The agricultural vinyl chloride resin film according to the present invention is excellent because it contains the components (A), (B), and (C) in a specific range as described above. It shows excellent weather resistance.

“Examples” The present invention will be explained in detail based on Examples below.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example/-1, Comparative Example/~t Polyvinyl chloride (P=/1100) 100 parts by weight Epoxy resin (manufactured by U.S. Shell Chemical Co., Ltd. Surface product name "EP-, rz♂") Barium-zinc-based extension stability Agent /, 3 #Barium stearate 0.2 #Ethylenebisstearamide 0. ．． 2 #Nrubitan Monostearate/, 6 1 In a different composition, (
Each of A) component, (B) component, and (C) component is
The amounts shown in the table were mixed.

These 72 types of compositions were stirred and mixed using a super mixer for 10 minutes, then kneaded for 10 minutes on a roll heated to /lj°C, and then formed into a film with a thickness of θ and /μ using an L-type calendar molding machine. Manufactured.

Various properties of each film were evaluated according to the methods described below. The evaluation results are listed in Table 1.

(a) Evaluation of weather resistance Facing south, against a flat surface! A large number of films were exposed on a window frame-shaped exposure test stand set up at an angle (location: Nagoyafu, Aichi Prefecture), and 1 month and 7 days had passed since the start of spreading.
After 2 and 1 months had elapsed, a portion of the film was removed from the exposure test stand and the appearance and residual elongation rate were evaluated.

The "weather resistance evaluation" criteria were as follows.

○・・・・・・No change in appearance, remaining elongation rate is x
Those with iq6 or higher.

○×・・・No change in appearance, remaining elongation rate is 10,
Within the range of t/%.

Δ・・・・・・Some changes in appearance such as discoloration are observed, and the residual elongation rate is in the range of 1rO-AI%.

Δ×: Appearance changes such as discoloration are partially observed, and the remaining elongation rate is in the range of to-da lq6.

×・・・・・・Discoloration is observed over the entire surface,
The remaining elongation rate is ≠04 or less.

Note that the residual elongation rate was calculated using the following formula.

(b) Evaluation of dust resistance For the evaluation of (a), each film was removed from the exposure test stand and the light transmittance at wavelength s s s microns was measured (with a Hitachi-made rupture spectrophotometer). ,
BPS-2U type is used).

From Table 1, the following becomes clear.

(1) The agricultural vinyl chloride film (Examples/~t) according to the present invention exhibits excellent weather resistance and dust resistance even when used outdoors for a long time.

(2) Component (A) essential in the film of the present invention,
If even one of the components (B) and (C) is missing, the dustproof properties and weather resistance of the film will deteriorate (Comparative Examples 1 and 2).

(3)Also, even if the three components are combined, if the total amount is too small (Comparative Example) or too large (Comparative Example 6), both dust resistance and weather resistance will deteriorate.

(4) Furthermore, a film in which the ratio of component (B) and component <a) of the three components is outside the range of //2 to -20// in terms of weight ratio (Comparative Example 3, Hiroshi), If the ratio is too small, no effect of improving dust resistance can be expected (Comparative Example 3), and if the ratio is too large, weather resistance will decrease (Comparative Example DA).

Claims (2)

[Claims] (1) In vinyl chloride resin, (A) Phthalate ester plasticizer represented by general formula (I), ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(I) (B) Phthalate ester plasticizer represented by general formula (II), ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(II) [In formula (I) and formula (II), R_1, R_2, R
Each of _3 represents a group selected from linear or branched alkyl groups of C_2 to C_1_3, and R_4 represents a group selected from aryl or cycloalkyl groups. [C) The three components of organic phosphate ester are blended within the range of 40 to 60 PHR, and the blending ratio of component (B) and component (C) is 1:2 to 20: 1. An agricultural vinyl chloride resin film characterized by being within the range of 1. (2) Claim (1) characterized in that the organic phosphate ester is tricylenyl phosphate.
Agricultural vinyl chloride resin film as described in .