JPH01235522A - Agricultural vinyl chloride-based resin film - Google Patents

Abstract

PURPOSE:To obtain a film excellent in heat retentivity and antifogging nature at low temperatures without impairing transparency, by incorporating a vinyl chloride resin with a compound having polyfluoroalkyl group and a hydrotalcite compound to limit light transmittance of the film. CONSTITUTION:The objective film can be obtained by incorporating a 100pts.wt. of a vinyl chloride-based resin with (A) 0.1-2pts.wt. of a polyfluoroalkyl group- contg. compound and (B) 0.1-15pts.wt. of a hydrotalcite compound of the formula (M<2+> is divalent metallic ion selected from Mg, Ca and Zn; A<n-> is n-valent anion; 0<x<0.5; 0<=m<=0.5). This film does not transmit the light <=350nm is wavelength, has a transmittance for the light 390nm in wavelength of >=50%, and transmits the light >=400nm in wavelength. Said film may further be incorporated, as needed, with other ingredients such as plasticizer, lubricant thermal stabilizer, antioxidant, antifogging ultraviolet light absorber, pigment or dye.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides an agricultural vinyl chloride resin film, which has excellent heat retention and antifogging properties at low temperatures without impairing transparency, and which also prevents crops from being damaged by pests. The present invention relates to an agricultural vinyl chloride resin film that can reduce the amount of damage.

(Prior Art) In recent years, greenhouse horticulture has been gradually increasing because it is possible to improve profits through forced cultivation or controlled cultivation of useful plants.

The covering materials used in greenhouse horticulture include polyethylene film, ethylene-vinyl acetate copolymer film, polycarbonate film, methyl methacrylate resin film, acrylic resin film, vinyl chloride resin film, and glass. .

Among them, agricultural vinyl chloride resin films containing a large amount of plasticizer are widely used because they are superior in light transmittance, heat retention, mechanical strength, weather resistance, etc. compared to other synthetic resin films.

However, in recent years, cultivation methods have become extremely diversified, with the aim of increasing profits by shipping harvested products during high-priced periods.

That is, in conventional greenhouse horticulture, harvest targets were set and cultivation schedules such as planting were established before open-field cultivated crops became available. However, because producers have traditionally used almost the same cultivation methods, the shipping times for the harvests almost overlap, and the shipping prices have to be low.

Due to the above reasons, methods are being adopted to further advance the planting period and ship products before general greenhouse horticulture products become available.

The reality is that when this type of cultivation is adopted, cultivation is naturally forced under extremely harsh conditions of severe cold.

However, during the cold season, the amount of sunlight is generally low, which creates extremely disadvantageous conditions for crop cultivation.

To address these problems, materials to which a far-infrared absorbing inorganic filler is added have been proposed in order to improve heat retention during the extremely cold season (Japanese Patent Application Laid-Open No. 170322/1983,
1-92514, JP-A-57-36144, JP-A-57-36916, etc.).

Although such materials have good heat retention properties, they are not sufficiently effective for crops that require a lot of light because of their low transparency.

On the other hand, JP-A-60-104141, JP-A-61-1
By adding a hydrotalcite compound as an inorganic filler as seen in Publication No. 11349, it is possible to create a material with excellent heat retention without impairing transparency! has been done.

[Problem to be solved by the invention]

However, although such materials have good heat retention properties, their anti-fogging properties at low temperatures are low, so it takes a long time for moisture inside the greenhouse to condense on the film surface in the morning, especially at low temperatures.
There was a problem that the amount of daylight was further reduced during the cold season when the amount of light was relatively low.

In addition, if heat retention is improved, crop growth will be promoted, and the warm interior of the greenhouse will make it easier for pests such as Thrinops, spider mites, and aphids to invade and breed (as a result, crops will suffer from pest and disease damage, reducing yields). There was also the problem of causing a decline.

Pesticides are generally used to combat such pest problems, but they are not sufficiently effective and there is also the problem of residual pesticides, so their use is restricted before harvest.

In addition, as seen in Japanese Patent Application Laid-Open No. 58-146227, by using a coating material that suppresses the transmission of light of a specific wavelength,
Although proposals have been made to reduce damage caused by pests, this material still lacks sufficient heat retention, making it insufficiently effective for crop growth when used in the coldest months.

When heating the inside of a greenhouse, a large amount of fuel was required.

As described above, a film that maintains the temperature inside the greenhouse without impairing transparency, has excellent antifogging properties at low temperatures, and can reduce damage caused by pests has not yet been developed.

An object of the present invention is to provide an agricultural vinyl chloride resin film that has excellent heat retention and antifogging properties at low temperatures without impairing transparency, and can reduce damage to crops from pests.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors found that a compound having a specific polyfluoroalkyl group,
The present inventors have discovered that by containing a specific amount of a specific hydrotalcite compound and further substantially blocking the transmission of light with a wavelength of 350 nm or less, the quality of crops can be improved and yields can be increased, leading to the completion of the present invention. .

That is, the present invention provides a compound having a polyfluoroalkyl group having 3 to 20 carbon atoms in a vinyl chloride resin and 0.01 to 2 parts by weight of the following formula (I) % formula % (I) (with the proviso that in the formula represents a divalent metal ion selected from the group consisting of Mg, Ca and Zn, 80- represents an n-valent anion, and X and m each satisfy the following conditions 0<x<
0.5, O≦m≦0.5) contains 10.1 to 15 parts by weight of a hydrotalcite compound, which substantially blocks the transmission of light with a wavelength of 350 nm or less, and has a content of 390 nI11. Transmittance of wavelength light is 50%
The present invention is an agricultural vinyl chloride resin film characterized in that it substantially transmits light having a wavelength of 400 nm or more.

As the vinyl chloride resin used in the present invention, not only polyvinyl chloride but also copolymers containing vinyl chloride as a main component can be used. Monomers that can be copolymerized with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid,
Examples include itaconic acid, acrylic acid, and methacrylic acid.

In the present invention, a compound having a polyfluoroalkyl group having 3 to 20 carbon atoms is used.

Examples of such fluorine compounds include compounds represented by the following formula -II.

(I) R, BP In this formula, Rt is a polyfluoroalkyl group having 3 to 20 carbon atoms, and B is -CO-1-3O! -, these R
,,B have the same meanings in the following general formulas.

(2) R,0H (3) Rf B N (R' 0) i-H In this formula, R1 represents -C2H4-, -C3H&-, R1 represents a hydrogen atom or a lower alkyl group, and n is 1 Represents an integer between ~30. These R1 and RZ have the same meaning in the following general formula.

(4)　H+CH-CHrh-R” C00C1lzRr In this formula, a represents an integer from 1 to 100.

(5) H+CH-(Jlf-)-T-+-C)I-
C) Izh-11"COOC) IJr C00(-
R'0+-r)1 In this formula, b represents an integer of 1 to 40, and C represents an integer of 1 to 100. b and C have the same meaning in the following general formula.

In this formula, R3 represents a hydrogen atom or a methyl group, Q represents a trifunctional organic group, and - represents -COO- or -C1hO-. R3, Q and - have the same meanings in the following general formulas.

f8) Rr COO In this formula, H represents a hydrogen atom, an alkali metal, an alkaline earth metal, -NH, and 0M has the same meaning in the following general formula.

(9) Rt BNR' coo gate 0ω Rf SO, M flll) Rt C) IzOC, %llZ, sOJ In this formula, haze represents an integer from 1 to 20, +11 has the same meaning in the general formula below. has.

021 MOxSCHCOOCHJrC)IzCOO
CHJr 03) Rf BNC-)1z*OP(OM)zR”
0 (I4) Rf BNCJJRz”・HX In this formula, HX represents halogen acid.

(I51Rt BNC!H4N″R3″·X-In this formula, X represents a halogen acid group, and has the same meaning in the following general formula.

82 Hl R1 The above fluorine compounds can be used alone or in combination of two or more. The required amount varies depending on the type of fluorine compound to be blended.

-S 0.0 per 100 parts by weight of vinyl chloride resin
1 to 2 parts by weight is preferable, more preferably 0.03 to 1 part by weight.
Parts by weight. If the amount is less than 0.01 part by weight, the low-temperature antifogging effect will be poor, and if it is more than 2 parts by weight, the film will tend to become cloudy.

The hydrotalcite compound used in the present invention is a substance represented by the above formula (+).

A specific example is Alcamizer 1 (M=Mg
, A=CO', n=2, m=0.5, x=0.33
) Alkamizer 2 (M=Mg,, A=GO3,
n = 2, m = 0.5, x = 0.33), etc. are commercially available.

The average grain size is preferably 5μ or less, more preferably 3μ or less.

If the average particle diameter exceeds 5 μm, the strength and transparency of the film will be significantly reduced, which is not preferable.

The amount of the hydrotalcite compound added is preferably 1 to 15 parts by weight per 100 parts by weight of the vinyl chloride resin,
More preferably, it is 2 to 7 parts by weight.

If the amount of the hydrotalcite compound added is greater than the above amount, the strength of the film will be significantly reduced and there is a risk that it will break during actual use. On the other hand, if the amount added is less than 1 part by weight, the expected heat retention properties cannot be obtained.

In addition to the above, the film of the present invention may contain other resin additives, such as plasticizers, lubricants, heat stabilizers, antioxidants, antifogging agents, ultraviolet absorbers, pigments, dyes, etc., as necessary. You can.

As a plasticizer, for example, moro-octyl phthalate,
Phthalic acid derivatives such as di2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diisodecyl phthalate, isophthalic acid derivatives such as diisooctyl phthalate, adipic acid derivatives such as moro-butyl adipate, dioctyl adipate, maleic acid derivatives such as di-n-butyl maleate;
Examples include citric acid derivatives such as tri-n-butyl citrate, itaconic acid derivatives such as motubutyl itaconate, oleic acid derivatives such as butyl oleate, and ricinoleic acid derivatives such as glycerin monolysyllate.

The above plasticizers are used singly or in combination of two or more,
The amount used is usually 30 to 60 parts by weight per 100 parts by weight of the vinyl chloride resin.

Examples of phosphoric acid ester plasticizers include tricresyl phosphate and tricylenyl phosphate.

The use of phosphate ester plasticizers is preferable from the viewpoint of improving weather resistance, and the amount used is usually 1 part vinyl chloride resin.
1 to 10 parts by weight per 00 parts by weight is suitable.

Epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid ester, epoxidized raw fat oil, epoxidized polybutadiene, esters of epoxy stearate such as methyl, butyl, 2-ethylhexyl, and stearyl, tris( Epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil butyl fatty acid, 3-(2
'-xenoxy)-1,2-epoxypropane, bisphenol A diglycidyl ether, vinylcyclohexene dieboxide, cyclopentene diepoxide, 3
．． Examples include 4-epoxy-5-methylcyclohexanecarboxylate.

The amount of these epoxy compounds used is vinyl chloride resin 1
0.5 to 7 parts by weight per 00 parts by weight is suitable.

Nonionic surfactants are good as antifogging agents.
For example, sorbitan surfactants such as sorbitan monostearate, sorbitan monopalmitate, and sorbitan monohenzoate, and products to which alkylene oxide is added, glycerin monolaurate, diglycerin monopalmitate, and glycerin monostearate. Examples include glycerin-based surfactants such as polyethylene glycol monostearate, polyethylene glycol-based surfactants such as polyethylene glycol monopalmitate, alkylene oxide adducts of alkylphenols, and esters of sorbitan and glycerin condensates with organic acids. It will be done. These surfactants can be used alone or in combination of two or more.

Examples of lubricants and heat stabilizers include polyethylene wax, liquid paraffin, stearic acid, zinc stearate, aliphatic alcohol, calcium stearate, barium stearate, barium ricinoleate, dioctyltin dilaurate, dioctyltin maleate, phenols, Examples include organic phosphite compounds and β-diketone compounds.

Various types of ultraviolet absorbers can be used, but hensitriazoles and benzophenones are preferred.

Examples of henctriazole ultraviolet absorbers include:
2- (2'-hydroxy-5'-methylphenyl)
henctriazole, 2-(2'-hydroxy-5
゛-Methylphenyl)-5-carboxylic acid butyl ester hensitriazole, 2-(2゛-hydroxy-5゛-methylphenyl)-5,6-dichlorobenzotriazole, 2-(2゛-hydroxy-5゛- methylphenyl)-5-ethylsulfonecitriazole, 2-(
2'-Hydroxy-5'-tert-butylphenyl)-5
-chlorobenzotriazole, 2-(2°-hydroxy-5′-tert-butylphenyl)benzotriazole,
2-(2°-hydroxy-5′, amyl phenyl)benzotriazole, 2-(2′-hydroxy-3″,
5'-dimethylphenyl)hencytriazole, 2-(
2'-hydroxy-3'', 5'-dimethylphenyl)
-5-methoxybenzotriazole, 2-(2'-methyl-4'-hydroxyphenyl)hencytriazole,
2-(2″-stearyloxy-3′,5′-dimethylphenyl)-5-methylbenzotriazole, 2-(2
'-Hydroxy-5°-carboxylic acid phenyl)hencytriazole ethyl ester, 2-(2'-hydroxy-31-methyl-5'-tert-butylphenyl)hencytriazole, 2-(2"-hydroxy-3',5 '
-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methoxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-phenylphenyl)-5-chlorobenzo Examples include triazole, 2-(2'-hydroxy-5'-cyclohexylphenyl)benzotriazole, and the like.

In addition, as benzophenone ultraviolet absorbers, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4-dihydroxybenzophenone , 2.2”-
Dihydroxy-4,4''-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2'-dihydroxy-4-methoxyhensiphenone, 2-hydroxy-4-methoxy-5-sulfonhensiphenone , 2,2°, 4,4'-tetrahydroxybenzophenone, 2,2'-hydroxy-4
゜4'-dimethoxy-5-sodium sulfobenzophenone, 4-dodecyloxy-2-hydroxybenzosiphenone, 2-hydroxy-5-chlorobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane, etc. can be exemplified.

These ultraviolet absorbers can be used alone or in combination of two or more. Further, the amount used is appropriately determined depending on the absorption characteristics of the ultraviolet absorber used.

The agricultural vinyl chloride resin film of the present invention contains a base vinyl chloride resin, a compound having a polyfluoroalkyl group having 3 to 20 carbon atoms, a hydrotalcite compound, and other resin additives as the essential components. A mixed resin composition formed into a film, which substantially blocks the transmission of light with a wavelength of 350 rv+ or less, has a transmittance of 50% or more of light with a wavelength of 390 nm, and is 400 n- or more. It substantially transmits light with a wavelength of .

In the present invention, "substantially blocking the transmission of light with a wavelength of 350 ns or less" means that the average transmittance of light with a wavelength of 290 to 35 nm, which is the shortest wavelength among sunlight that reaches the ground, is 100 ns or less.
% complete blocking, but also includes allowing transmission of light of the wavelength up to an average transmittance of up to 15%, preferably 10% or less.

Furthermore, "substantially transmitting light with a wavelength of 400 nm or more" means not only completely transmitting 100% of light with a wavelength of 400 nm or more, but also allowing transmission of light with an average transmittance of 60% or more. It includes things.

If light with a wavelength of 350 rv or less is transmitted, the invasion of pests into the greenhouse becomes significant, which adversely affects the crops and reduces the quality of the crops.

On the other hand, the transmittance at 390 nm is 50% or more, and
If light of nm or higher is not substantially transmitted, pests can be prevented from entering the greenhouse, but the crops may grow too long.
The color of the skin and leaves of the harvested fruit becomes pale, reducing its commercial value.

The basic vinyl chloride resin composition is a vinyl chloride resin mixed with a compound having a polyfluoroalkyl group having 3 to 20 carbon atoms, a hydrotalcite compound, and other resin additives, and is used in ribbon blenders, Banbury mixers, etc. −
, super mixer, Henschel mixer, etc.

The film according to the present invention is produced from the above composition using known film forming techniques. Known film-forming techniques include calendar molding, T-die extrusion, inflation molding, and solution casting.

If the thickness of the film related to the present invention is too thin, the strength will be insufficient, which is undesirable.On the other hand, if it is too thick, it will be difficult to make the film into a film or perform other handling (cutting the film and joining it into a house shape, etc.) (including the work of expanding the frame), etc., so it is usually 0.03 to 0.
．． A suitable length is 3 m, preferably 0.05 to 0.2 mm.

The film according to the present invention has a transparent dustproof layer made of acrylic resin, fluorine-containing resin, urethane resin, etc. on at least one side of the film in order to maintain high transparency over a long period of time. Good too.

[Example] The present invention will be explained below with reference to Examples.

Examples 1 to 3, Comparative Examples 1 to 4 Table 1 Basic formulation To the basic formulation shown in Table 1 above, fluorine compounds, hydrotalcite compounds, and ultraviolet absorbers were added in the types and amounts shown in Table 2, After mixing for 10 minutes with a Henschel mixer, the mixture was kneaded at 165°C, and then an agricultural vinyl chloride resin film with a thickness of 0.1 m (hereinafter abbreviated as agricultural pipe) was obtained using an L-type calender.

Regarding agricultural vinyl, the light transmittance by wavelength is shown in Figure 1, and the measurement results of low-temperature antifogging properties, heat retention properties, and film appearance are shown in Table 2.

We also investigated the growth status of crops during actual cultivation, the quality of harvested fruits, and the occurrence of pests, and the results are also shown in Table 2.

1. Method (I) Light transmittance by wavelength Measure the light transmittance by wavelength of each film using a self-recording spectrophotometer.
It was measured using lV-200 (■ manufactured by Kansei Seisakusho).

(2) Anti-fogging properties at low temperatures Place each film in a wooden frame whose top surface has an inclination of 10 degrees, fill it with 20°C water, and place it in a low-temperature bath keeping the outside temperature at O'C. The frame was submerged to a depth of 174 m below the water surface.

Thereafter, the state of water condensation on each film was observed over time.

Surface condition: 1. When the film is completely cloudy due to condensed water droplets. A score of 5 was given when the film was completely transparent and had no cloudy areas.

Flow start time: The time at which condensed water droplets started flowing along the film was observed.

(3) Heat retention Six open-air tunnels with a width of 1 m and a length of 2 m were constructed in a field in Nagoya City, Aichi Prefecture, each tunnel was covered with a film, and the temperature inside the tunnel at night was measured at the center of the tunnel. The temperature measurement period is from February 15th to February 24th.
For day 0, the temperature was measured every 30 minutes from 6:00 pm to 6:00 am the next morning, and the temperature during this period was averaged to be the daily average value, and the average value for 10 days was further averaged. Indicated.

(4) Film appearance The film was placed on a window frame-shaped exposure test stand tilted 15 degrees to the south (
Installed at the installation location (Nagoya City) for a specified period (Table 2).
(See) After the elapsed time, the appearance of the film was visually judged.

O: No change.

Δ: Slight brown spots are observed.

×: Brown spots are observed.

(5) Cultivation test A pipe house with a frontage of 5 m and a length of 25 m was constructed in Ueki-cho, Kumamoto Prefecture, and after covering it with each film, watermelon (variety: Fuji Hikari) was planted in mid-February, using a non-heating method. cultivated in
The growth condition of watermelon during the cultivation period and the quality of harvested fruit were evaluated.

■Growth status O: Growing smoothly and with good ball fat.

Δ: Slightly delayed and balls are slightly small.

■Harvested fruit quality Q: Both shape and coloring are good.

Δ: Slightly inferior in shape and coloring.

×: Poor coloring.

■ Infection status of pests During the cultivation period, the number of pests (Surisopus, spider mites) occurring on 50 leaves in each plot was investigated and expressed as the number of pests occurring per plant.

〔Effect of the invention〕

As is clear from the above examples, the film of the present invention has improved heat retention due to the addition of a hydrotalcite compound.

Additionally, since a specific fluorine compound is added, anti-fogging properties at low temperatures are improved.

Furthermore, since the transmission of light with a wavelength of 350 nm or less is blocked, damage caused by pests such as Thrilapse and spider mites is reduced.

On the other hand, if the transmission of light with a wavelength around 390 nm is blocked, the occurrence of pests can be suppressed, but the skin of the watermelon will become pale in color.

The agricultural vinyl chloride resin film according to the present invention has the following effects and greatly contributes to greenhouse horticulture.

■Good heat retention allows crops to grow better.

■Since it has good heat retention, energy savings can be expected.

■Since it uses an inorganic filler, it is less sticky and can be opened and closed for ventilation in tunnels, greenhouses, etc. efficiently.

■Good anti-fogging properties at low temperatures allow a large amount of light to pass into the greenhouse, resulting in good crop growth.

■The quality of the harvest is good because there are fewer pests.

■Since it has good weather resistance, it can be reused.

[Brief explanation of the drawing]

FIG. 1 is a diagram of the light transmittance by wavelength of agricultural products of Examples of the present invention and Comparative Examples.

Claims (1)

[Claims] 1. 0.01 to 2 parts by weight of a compound having a polyfluoroalkyl group having 3 to 20 carbon atoms in a vinyl chloride resin and the following formula (I) M^2^+_1_-_xAl_x(OH)_2 (A^n
^-)_x_/_n・mH_2O(I) (However, M in the formula
^2^+ indicates a divalent metal ion selected from the group consisting of Mg, Ca, and Zn, A^n^- indicates an n-valent anion, and x and m each satisfy the following conditions 0<x<0 .5, 0≦m≦0.5) contains 0.1 to 15 parts by weight of a hydrotalcite compound represented by An agricultural vinyl chloride resin film having a light transmittance of 50% or more and substantially transmitting light having a wavelength of 400 nm or more.