JPH05320452A - Vinyl chloride resin film for agricultural use - Google Patents

Abstract

(57) [Summary] [Structure] For 100 parts by weight of vinyl chloride resin, o-
Cresol novolac glycidyl ether 0.1-1
0 parts by weight and general formula (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are chain or cyclic hydrocarbon groups which may have an oxygen atom interposed therebetween, X is an alkylene group having 1 to 6 carbon atoms, and an oxygen atom. , A sulfone group or a sulfide group, and a represents 0 or 1), which is a vinyl chloride resin film for agricultural use containing 0.1 to 10% by weight of a phosphoric acid ester compound. [Effect] Excellent in plate-out property during processing, stain resistance, cold resistance, weather resistance and dust resistance, suitable for house and tunnel cultivation, etc., and excellent durability that can be used for a long period of time. Have sex.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a plate-out property during processing, which is suitable for use in greenhouses and tunnel cultivation.
Excellent in antifouling property, cold resistance, weather resistance and dust resistance,
The present invention relates to a novel agricultural vinyl chloride resin film having excellent durability that can be used for a long period of time.

[0002]

2. Description of the Related Art Agricultural film based on a vinyl chloride resin film for agricultural use has a degree of difference depending on the purpose of use and the place of use. After two years, the dust-proof property of the outer surface of the house or tunnel deteriorates, making it unusable. For example, it is known that an agricultural vinyl chloride resin film is blended with tricresyl phosphate as a plasticizer in order to impart long-term weather resistance.However, in this product, the plasticizer exudes during use and dust is generated. It has a drawback that it is easily adhered and the dustproof property is lowered. Further, there is known a product containing an epoxy resin compound having bisphenol A as a skeleton for the same purpose, but this product has a drawback that the plate-out property during processing is not good.

[0003]

SUMMARY OF THE INVENTION The present invention overcomes the disadvantages of the conventional dustproof agricultural resin film,
A novel agricultural vinyl chloride resin film with good plate-out resistance, excellent antifouling properties, cold resistance, weather resistance, and dust resistance, and excellent durability that can be used for a long period of time. It was made for the purpose of doing.

[0004]

The inventors of the present invention have conducted various studies to develop an agricultural vinyl chloride resin film having the above-mentioned preferable characteristics, and as a result, the vinyl chloride resin has a predetermined amount of o. -It was found that the purpose can be achieved by using a glycidyl ether of -cresol novolac and a specific phosphoric acid ester compound together, and based on this finding, the present invention has been completed.

That is, the present invention relates to a vinyl chloride resin 1
(A) 0.1 to 10 parts by weight of glycidyl ether of o-cresol novolac and (B) the general formula

[Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are chain or cyclic hydrocarbon groups which may have an oxygen atom interposed therebetween, X is an alkylene group having 1 to 6 carbon atoms, and an oxygen atom. , A sulfone group or a sulfide group, and a represents 0 or 1) 0.1 to 10% by weight of a phosphoric acid ester compound represented by formula (1) is provided, and a vinyl chloride resin film for agriculture is provided. ..

Examples of the glycidyl ether of o-cresol novolac as the component (A) to be blended with the vinyl chloride resin in the present invention include ESCN-220 (manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 200 to 230 g / eq.,
Softening point 75 to 83 ° C.) YDCN-703 (manufactured by Tohto Kasei Co., epoxy equivalent 200 to 230 g / eq., Softening point 7
Commercially available products such as 5 to 85 ° C.) are used.

Further, in the phosphoric ester compound represented by the formula (I) which is the component (B) to be blended with the vinyl chloride resin, the "oxygen atom is mediated by R ₁ , R ₂ , R ₃ and R ₄ " May be a chain or cyclic hydrocarbon group "
Examples of such groups include saturated or unsaturated aliphatic or alicyclic hydrocarbon groups, aromatic hydrocarbon groups or a combination of both, or groups corresponding to these having an ether bond in the chain. Are as illustrated below.

Alkyl groups such as butyl, hexyl, octyl, nonyl, decyl and tridecyl, alkenyl groups such as hexenyl and oleyl, cycloalkyl groups such as cyclohexyl, cycloalkenyl groups such as cyclohexynyl, aryl groups such as phenyl and naphthyl. , Alkoxyalkyl groups such as methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, isobutoxyethyl, hexoxyethyl, octoxyethyl, methoxypropyl, butoxypropyl, methoxybutyl, octoxybutyl, cyclohexoxyethyl, 2-ethylcyclohexoxy Cyclohexoxyalkyl groups such as ethyl, cyclohexoxybutyl, 2-ethylcyclohexoxybutyl, methoxycyclohexyl, ethoxycyclohexyl, butoxysic Hexyl, groups having the the ether linkage derived from ethers such as dibutylene glycol monomethyl cyclohexyl ether.

Among these groups, particularly preferable are hydrocarbon groups containing a saturated or unsaturated 6-membered carbon ring such as phenyl group, phenyl-lower alkyl groups such as benzyl and phenylethyl, cresyl and xylyl. , Lower alkyl-phenyl groups such as ethylphenyl and t-butylphenyl, and cycloalkyl groups such as cyclohexyl.

The "alkylene group having 1 to 6 carbon atoms" represented by X in the formula (I) is particularly

[Chemical 3] (In the formula, R ′ and R ″ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group, provided that the total number of carbon atoms of R ′ and R ″ is 5 or less.) An alkylene group of the type represented by is preferable, and specific examples thereof include the following.

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

In the above formula (I), X is particularly

[Chemical 9] , -CH ₂ - and -SO ₂ - are preferred.

Typical examples of the phosphoric acid ester compound represented by the general formula (I) used in the present invention are shown below.

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical formula 12]

[0021]

[Chemical 13]

[0022]

[Chemical 14]

[0023]

[Chemical 15]

[0024]

[Chemical 16]

[0025]

[Chemical 17]

[0026]

[Chemical 18]

[0027]

[Chemical 19]

[0028]

[Chemical 20]

[0029]

[Chemical 21]

[0030]

[Chemical formula 22]

[0031]

[Chemical formula 23]

[0032]

[Chemical formula 24]

[0033]

[Chemical 25]

[0034]

[Chemical formula 26]

[0035]

[Chemical 27]

[0036]

[Chemical 28]

[0037]

[Chemical 29]

[0038]

[Chemical 30]

These may be used alone or in combination of two or more. The phosphate compound represented by the formula (I) may be produced by any method,
Although a reaction product containing the compound represented by the formula (I) can be used, a pure product is preferable.

The phosphoric acid ester compound is, for example, a diphenol compound having a basic skeleton of the formula (I) (for example, bisphenol A) and an organic phosphorochlorate having groups corresponding to R ₁ , R ₂ , R ₃ and R _4. Is dissolved in an aromatic solvent such as benzene or toluene in a predetermined amount and reacted at about 40 to 80 ° C. in the presence of a dehydrochlorinating agent such as triethylamine, or with a hydroxy compound having a group corresponding to R _{1 to} R _4. It is produced by mixing with a diphenol compound and then adding phosphorus oxychloride to cause a reaction or a transesterification reaction.

In the present invention, the use ratio of the component (A) can be changed according to the type and the type of the component (B) used in combination, but it is 0.1% to 100 parts by weight of the vinyl chloride resin. 1 to 10 parts by weight, preferably 0.5 to 5
It is selected within the range of parts by weight. The ratio of the component (B) used can be changed depending on the type and the type of the component (A) used in combination, but is 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Preferably 0.5-5
It is selected within the range of parts by weight. If the proportion of the component (A) is too small, the weather resistance will be poor, and if it is too large, the film will be white and the commercial value will be reduced. If the proportion of the component (B) is too small, the weather resistance will be poor, and if it is too large, the workability will be poor.

The vinyl chloride resin as the base of the film of the present invention has, for example, a number average degree of polymerization of about 800 to 2
500, preferably about 1000 to 1800 polyvinyl chloride, a copolymer mainly composed of vinyl chloride (for example, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, vinyl chloride-halogenated olefin copolymer). Etc.) or other compatible resins based on these polyvinyl chloride or vinyl chloride copolymers (eg polyester resin, epoxy resin, acrylic resin, vinyl acetate resin, urethane resin, acrylonitrile-styrene-butadiene copolymer) And a blend with partially saponified polyvinyl alcohol). These vinyl chloride resins may be obtained by any conventional production method such as bulk polymerization method, emulsion polymerization method, suspension polymerization method and solution polymerization method. These vinyl chloride resins may be used alone or in combination of two or more.

For the vinyl chloride resin,
30 to 70 parts by weight, preferably 40 to 60 parts by weight, and 0.5 to 7 parts by weight, preferably 1.0 to 5.0 parts by weight, of lubricant and / or heat stabilizer per 100 parts by weight thereof. ;
0 to 5.0 parts by weight, preferably 1.0 to 4.0 parts by weight of antifogging agent or surfactant; 0 to 1% by weight, preferably 0.1.
0 to 3.0 parts by weight, preferably 0.1 to 0.5 parts by weight of ultraviolet absorber; 0 to 5.
0 parts by weight, preferably 0.1 to 1.0 parts by weight of an anti-sticking agent can be added.

Examples of the plasticizer include di-n-octyl phthalate, di-2-ethylhexyl phthalate,
Phthalic acid derivatives such as diisononyl phthalate and diisodecyl phthalate; Isophthalic acid derivatives such as diisooctyl isophthalate; Adipic acid derivatives such as dioctyl adipate; Others tricresyl phosphate, trixylenyl phosphate, epoxidized soybean oil, etc. Phthalate, dioctyl adipate and epoxidized soybean oil are suitable.

Examples of the lubricants or heat stabilizers include polyethylene wax, fatty acid amide, stearic acid, zinc stearate, barium stearate, calcium stearate, barium ricinoleate, chelators such as organic phosphites, epoxy resins and the like. Is mentioned.

The antifogging agent or surfactant may be any of those usually used, for example, a partial ester of polyhydric alcohol consisting of polyhydric alcohol and higher fatty acids is preferable. Specific examples of such substances include, for example, sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate,
A sorbitan-based surfactant such as an ester of a condensate of sorbitan and glycerin and a higher fatty acid and an ester of a condensate of sorbitan and an alkylene glycol and a higher fatty acid;
Glycerin-based surfactants such as glycerin monolaurate, glycerin monostearate, diglycerin monostearate, diglycerin monolaurate, diglycerin monopalmitate, triglycerin monostearate, tridiglycerin monostearate; polyethylene glycol monostearate Polyethylene glycol-based surfactants such as stearate, polyethylene glycol monopalmitate, polyethylene glycol alkylphenyl ether; other trimethylolpropane-based surfactants such as trimethylolpropane monostearate; pentaerythritol monopalmitate, pentaerythritol monostearate , Pentapentaerythritol-based surfactants such as dipentaerythritol monostearate; or isomers thereof Or the like can be mentioned those containing.

Examples of the above-mentioned antifogging agent include polymers containing a perfluoroalkyl group or a perfluoroalkenyl group, or low molecular weight fluorine-containing surfactants, and generally, at least 0.001% by weight, preferably Has a solubility in water of at least 0.01 wt.
In the above, those having the ability to reduce the surface tension of water to 35 dyn / cm or less, preferably 30 dyn / cm or less are preferable. Further, the perfluoroalkyl group may have an oxygen atom interposed in its carbon chain.

Examples of commercially available products used as the above-mentioned anti-fog agent include Unidyne DS-401, Unidyne D
S-403, Unidyne DS-451 (above, manufactured by Daikin Industries, Ltd.), Megafac F-142D, Megafac F-177 (above, manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-170, Florard FC-176, Fluorard FC-430 (above, Sumitomo 3M), Surflon S-141, Surflon S-145, Surflon S-381, Surflon S-382, Surflon S-3.
93 (above, manufactured by Asahi Glass Co., Ltd.) and the like.

As the ultraviolet absorber, for example, a benzotriazole type, benzophenone type, salicylic acid type or the like is used. The benzotriazole type compounds include 2- (2'-hydroxy-3 ', 5'-di-te
rt-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) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-te
rt-Butylphenyl) benzotriazole, 2-
(2'-Hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5 '-(1,
1,3,3-tetramethyl) phenyl] benzotriazole and the like.

As the benzophenone type,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-
Examples include hydroxy-4-octoxybenzophenone.

Examples of salicylic acid compounds include phenyl salicylate and paraoctyl phenyl salicylate.

These ultraviolet absorbers may be used alone or in combination of two or more, and benzotriazole type and benzophenone type are particularly preferable.

Further, other usual resin additives such as a filler, an antioxidant, an antistatic agent, a colorant and the like can be contained as required. The filler is usually used for suppressing stickiness of the film or maintaining the heat retention property, and as such, it is preferable to use silica, talc, aluminum hydroxide, hydrotalcite, calcium sulfate, silicic acid. Calcium, calcium hydroxide, magnesium hydroxide, kaolin clay, mica, alumina,
Examples thereof include inorganic ones such as magnesium carbonate, sodium aluminate, conductive zinc oxide, lithium phosphate, zirconium hydroxide. The type and amount of the filler are determined depending on the thickness of the film, but usually 0.05 to 7% by weight, preferably 0.1 to 5% by weight, based on the vinyl chloride resin of the base material. Used in a range.

In order to mix each of the above-mentioned vinyl chloride resins with each resin additive, the required amount is weighed and charged into a ribbon blender, a Banbury mixer, a super mixer or other conventionally known compounding machine or mixer and kneading. Good.

The resin composition thus obtained is prepared by a method known per se, for example, a calendering method, an extrusion molding method,
It can be formed into a film by a solution casting method or the like.

If the thickness of the film of the present invention is too thin, the strength will be insufficient, and if it is too thick, on the other hand, it will be inconvenient for film forming work and the like. Preferably 0.05 to 0.2 m
A range of m is suitable.

[0057]

INDUSTRIAL APPLICABILITY The agricultural resin film of the present invention is excellent in plate-out property during processing, antifouling property, cold resistance, weather resistance and dust resistance, and has excellent durability that can be used for a long period of time. Since it has, it is suitably used for greenhouses and tunnel cultivation.

[0058]

The present invention will be described in more detail with reference to Examples. The characteristics of each sample were visually evaluated by the following test methods or evaluation criteria.

(1) Cold resistance: Using a film impact tester with a thermostat (manufactured by Toyo Seiki Co., Ltd.), the brittle fracture rate measured at -18 ° C was evaluated as follows. ◯: less than 50%, x: 50% or more

(2) Plate-out resistance: surface temperature 18
0 ℃, Roll gap 0.4mm, Roll speed 20rpm
100 g of the sample was put into the 8-inch roll machine adjusted to 1, and the roll was kneaded, and the stain state of the roll surface after 20 minutes was visually evaluated as follows. ○: Good, △: Slightly soiled, ×: Remarkably soiled

(3) Weather resistance: The sample was exposed to an outdoor exposure table for 12 months, and the tensile rupture strength measured based on JIS-K-6732 was evaluated as follows. ◯: 2.5 kg / mm or more, Δ: 2.0 to 2.5 kg /
mm, x: less than 2.0 kg / mm

(4) Dustproofness: Exposure was performed on an outdoor exposure table at an angle of 20 degrees for 6 to 24 months, and the appearance was judged according to the following evaluation criteria. ○: Not much different from the initial state of exposure, △: A little dust is attached, ×: Dust is significantly attached

Examples 1 to 4 and Comparative Examples 1 to 3 Each component shown in Table 1 was blended, and a 0.1 mm thick vinyl chloride resin film sample was calendered at 190 ° C. using four calender rolls. It was made. The characteristics of the obtained sample were evaluated and the results shown in Table 1 were obtained.

[0064]

[Table 1]

Note: 1) Sumitomo Chemical Co., Ltd. (epoxy equivalent: 200-230 g / eq., Softening point: 75-83)
2) Toto Kasei Co., Ltd. (Epoxy equivalent: 200-230 g)
/ Eq. , Softening point: 75-85 ° C)

3) Formula (X)

[Chemical 31] (R is a p-methylphenyl group)

4) Formula (Y)

[Chemical 32] (R ₁ is a 3,4-dimethylphenyl group)

5) Sumitomo Chemical Co., Ltd. (bisphenol A
Type, epoxy equivalent: 184 to 194 g / eq. , 25 ℃
Viscosity at 11,000 to 14,000 cp. )

As a result, regarding the film samples of Comparative Examples, the respective characteristics of Comparative Examples 1 and 2 were not good, and those of Comparative Examples 3 and 4 were partially favorable in terms of plate-out property or cold resistance. Although the results can be seen, it can be seen that all the properties of the film of the present invention are excellent, while the other properties are not good and they cannot be put to practical use.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08L 63:00)

Claims (1)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
(A) 0.1-10 parts by weight of glycidyl ether of o-cresol novolac and (B) general formula: (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are chain or cyclic hydrocarbon groups which may have an oxygen atom interposed therebetween, X is an alkylene group having 1 to 6 carbon atoms, and an oxygen atom. , A sulfone group or a sulfide group, and a represents 0 or 1). A vinyl chloride resin film for agricultural use, comprising 0.1 to 10% by weight of a phosphoric acid ester compound represented by the formula.