JPH04272946A - Agricultural polyolefin resin film - Google Patents

Abstract

PURPOSE:To provide an agricultural polyolefin resin film excelling in the persistence of antifogging and anticlouding effects and being good in transparency. CONSTITUTION:An agricultural polyolefin resin film prepared by mixing a polyolefin resin with a fluorine compound, a nonionic surfactant and a hindered amine compound in a specified ratio and forming the mixture into a film.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyolefin resin films for agricultural use. More specifically, the present invention relates to an agricultural polyolefin resin film that has excellent transparency, anti-fog properties, and long-lasting anti-fog properties.

0002

[Prior Art] In recent years, agricultural vinyl chloride films, polyethylene, ethylene-vinyl acetate copolymers, and polyolefin resins have been used to increase the marketability and productivity of agricultural crops through semi-forced or controlled cultivation. So-called greenhouse cultivation and tunnel cultivation, in which useful crops are cultivated under agricultural covering materials such as special films, are widely practiced. Among these, special films made mainly of polyolefin resins do not contain plasticizers and have a stable chemical structure, so their light transmittance remains almost unchanged even after long-term use, and they are not harmful even when incinerated. It has become popular in recent years because it does not generate gas and is inexpensive.

[0003] Recently, especially with the trend towards energy saving,
In order to effectively utilize solar energy without adversely affecting the crops inside the greenhouse, management techniques are being used to seal the greenhouse as tightly as possible and insulate it with curtains. This management tends to make the temperature inside the greenhouse more humid than before, and at the same time, there is a problem in that the amount of fog (also called mist) that occurs inside the greenhouse increases significantly. Fog is said to be closely related to the pests and diseases of cultivated crops, as well as the quality and yield of crops.
It is said that this must be avoided as much as possible in greenhouse cultivation.

[0004] Fog is basically generated by the condensation of water vapor inside a greenhouse, and is a phenomenon that often occurs in the morning and evening when the temperature difference inside and outside the greenhouse changes rapidly. Fog can be eliminated by ventilating the air inside and outside the house. However, since the heat retention of greenhouses is generally emphasized, ventilation is often not possible, which has been a major problem. Since the generation of fog is essentially a phenomenon caused by moisture within the greenhouse, the generation of fog can be reduced by reducing the amount of moisture supplied to the atmosphere within the greenhouse. One way to prevent fog is to cover the soil surface inside the greenhouse with mulch material. However, using mulch materials not only complicates the covering work but also increases material costs, so it is not necessarily a beneficial method for greenhouse growers.

[0005] As another countermeasure against fog, that is, a method for reducing the generation of fog by improving coating materials, a method has been proposed in which an organic siloxane compound is added to the coating material. Although the film has anti-fog performance, it suffers from significant bleed-out and has poor transparency and durability of anti-fog performance. In addition, Japanese Patent Application Laid-Open No. 58-32644 discloses a method of adding a fluorine compound to a polyolefin resin film, but although these methods improve the anti-fog durability to some extent, they do not cause bleed-out of the anti-fog agent. However, there are disadvantages such as a decrease in antifogging durability, whitening of the film, and decrease in transparency.

[0006]

[Problems to be Solved by the Invention] An object of the present invention is to provide a satisfactory agricultural polyolefin resin film that has good anti-fog and anti-fog properties and good transparency. It is something.

[0007]

[Means for Solving the Problems] The present inventors have discovered that a specific fluorine-containing compound and a surfactant are added to a polyolefin resin.
Furthermore, the present invention was completed based on the discovery that a film with good transparency and excellent anti-fog and anti-fog properties can be obtained by using a specific amount of a hindered amine compound. That is, the gist of the present invention is that per 100 parts by weight of polyolefin resin, 0.01 to 2 parts by weight of a fluorine-containing compound, 0.5 to 5 parts by weight of a nonionic surfactant, and 0.05 to 5 parts by weight of a nonionic surfactant. This is an agricultural polyolefin resin film characterized by being blended with part by weight of a hindered amine compound.

The present invention will be explained in detail below. The polyolefin resin that can be used in the present invention includes α-
Homopolymers of olefins, copolymers with different monomers mainly composed of α-olefins, such as polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-4-methyl -1-
Examples include pentene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, and ionomer resins.

Among these, the density ranges from 0.910 to 0.910.
935 polyethylene or ethylene-α-olefin copolymer and ethylene-α-olefin copolymer with a vinyl acetate content of 30% by weight or less
Vinyl acetate copolymers are preferred from the viewpoints of transparency, weather resistance, and cost. Furthermore, those having a vinyl acetate content of 3 to 20% by weight are more preferable. The fluorine-containing compound that can be blended into the present invention is included in the category of so-called surfactants, and instead of H bonded to C of the hydrophobic group of ordinary surfactants, part or all of it is F. Among surfactants substituted with , surfactants containing a perfluoroalkyl group or a perfluoroalkenyl group are particularly preferred.

[0010] Examples of the fluorinated surfactants that can be used in the present invention include anionic fluorinated surfactants (Nos. 1 to 4 in Table 1) and cationic fluorinated surfactants (Nos. 5 and 6 in Table 1). , amphoteric fluorosurfactant (No. 7 in Table 1)
), nonionic fluorosurfactant (No. 8, 9 in Table 1)
), and representative examples are shown in Table 1. Examples of suitable fluorosurfactants of the type shown in Table 1 or other types are as follows.

1) In the Cn F2n+1COOM formula, M=
Hydrogen atom, alkali metal, -NH4, n=5-12,
Preferably 6 to 10, for example C9 F19COONa
,C8F17COOLi 2)Cn F2n+1CONH(C2 H4O)m H
In the formula, n=5-12, preferably 6-10, m=1-3
0, preferably 2-20, e.g. C9 F19CON
H(C2H4O)3H

[Chemical formula 1] 4) Cn F2n+1CONHC3 H6 N+(CH
3)2C2H4COO- where n=5-12, preferably 6-10, e.g.
8 F17CONHC3 H6 N+(CH3)3
C2 H4 COO- 5)Cn F2n+1CONHC3 H6 N+(CH
3)2 ・X-In the formula, X = halogen acid group, n = 5-1
2, preferably 6 to 10, e.g. C8 F17CON
HC3 H6 N+(CH3)3 ・I- 6)Cn F2n+1(CH2)m COOM formula,
M=hydrogen atom, alkali metal, -NH4, n=3-1
2, preferably 5-10, m=1-16, preferably 2
~10, e.g. C7F15(CH2)5COO
Na,C8 F17(CH2)4COOK7)Cn
F2n+1SO2 N(C2 H5 )C2 H4
OPO(OH)2 where n=5-12, preferably 6-10, e.g.
8 F17SO2 N(C2 H5 )C2 H4 O
PO(OH)2 8)Cn F2n+1SO2 N(C
2 H5 ) CH2 COOM, where M = hydrogen atom, alkali metal, -NH4, n = 5 to 12, preferably 6
~10, e.g. C8 F17SO2 N(C2 H5
)CH2 COOK 9)Cn F2n+1SO2 N(C2 H5 )C2
In the H4 OSO3 H formula, n=5-12, preferably 6-10, for example, C8 F17SO2 N(C2 H
5) C2 H4 OSO3 H10) Cn F2n
+1SO2N(C2H5)(C2H4O)m
H where n=5-12, preferably 6-10, m=1-3
0, preferably 2-20, e.g. Cn F2n+1S
O2N(C2H5)(C2H4O)14H

[
The above-mentioned fluorine-containing compounds may be one or two types.
You may use combinations of more than one species. The blending amount of the fluorine-containing compound is 10% of the polyolefin resin as an active ingredient.
It is within the range of 0.01 to 2 parts by weight relative to 0 parts by weight. If the blending amount is less than 0.01 part by weight, the anti-fog property will not be sufficiently developed. If it exceeds 2 parts by weight, it becomes difficult to knead into the polyolefin resin, bleed-out becomes significant, and transparency and dustproof properties are reduced, which is not preferable.

Examples of the nonionic surfactant used in the present invention include sorbitan monomyristate,
Sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate and/or 0.1~
Sorbitan surfactants such as 5 mol alkylene oxide adducts; glycerin monopalmitate, glycerin monostearate, glycerin dipalmitate, glycerin distearate, diglycerin monostearate,
diglycerine monobehenate, diglycerine dipalmitate, diglycerine distearate, diglycerine monopalmitate monostearate, triglycerine monostearate, triglycerine distearate, triglycerine tristearate and/or 0. Glycerin surfactants such as 1 to 5 moles of alkylene oxide adducts; polyethylene glycol surfactants such as polyethylene glycol monostearate and polyethylene glycol monopalmitate; trimethylolpropane interfaces such as trimethylolpropane monostearate Activators; pentaerythritol surfactants such as pentaerythritol monopalmitate; alkylene oxide adducts of alkylphenols; esters of sorbitan/glycerin condensates and fatty acids, esters of sorbitan/alkylene glycol condensates and fatty acids, etc. mentioned,
These can be used alone or in combination of two or more.

Particularly useful surfactants for the present invention include sorbitan and/or glycerin surfactants such as sorbitan monostearate, glycerin monostearate, and diglycerin distearate. The amount of such an antifogging agent is within the range of 0.5 to 5 parts by weight. If it is less than 0.5 parts by weight, the antifogging property will not be sufficiently developed, and if it exceeds 5 parts by weight, it will tend to bleed out.
This is not preferable because it reduces the transparency and dustproof properties of the film.

[0015] As the hindered amine compound, various compounds commonly used for agricultural purposes can be used. Specifically, JP-A-62-59745, column 5, line 37 to column 16, line 18, JP-A-2-30529
It is a hindered amine compound described on page 20, line 15 to page 38, line 3 of the specification. Examples of commercially available hindered amine compounds that can be used in the present invention include:
TINUVIN770, TINUVIN780, TIN
UVIN144, TINUVIN622LD, CHIM
ASSORB119FL, CHIMASSORB944
(all manufactured by Ciba Geigy), Sanol LS-765 (
Sankyo Co., Ltd.), MARKLA-63, MARK L
A-68, MARK LA-62, MARK LA
-67, MARK LA-57 (manufactured by Adeka Argus), and the like.

These hindered amine compounds can be used alone or in combination of two or more. The blending amount is 0.0 parts by weight per 100 parts by weight of the polyolefin resin.
It is within the range of 5 to 5 parts by weight. If the blending amount is less than 0.05 parts by weight, bleed-out to the film surface will increase, the transparency of the film will deteriorate, and the anti-fog and anti-fog durability will also decrease significantly, and if the amount exceeds 5 parts by weight, in case of,
Anti-fog and anti-fog properties at low temperatures are no longer achieved. Therefore,
The blending amount is in the range of 0.05 to 5 parts by weight, preferably 0.2 to 2 parts by weight.

Furthermore, among these hindered amine compounds, those having a molecular weight in the range of 700 to 4,000 are more preferable. If the molecular weight is less than 700, the resin itself tends to bleed out, resulting in a decrease in transparency and a decrease in anti-fog and anti-fog properties at low temperatures. Furthermore, if the molecular weight exceeds 4000, the dispersibility in the polyolefin resin will be poor and the transparency will be reduced, which is not preferable. Further, the agricultural polyolefin resin film of the present invention may contain the following various additives as necessary.

That is, plasticizers such as di-2 ethylhexyl phthalate and di-2 ethylhexyl adipate,
Organic phosphate esters such as tricresyl phosphate and tricylenyl phosphate, organic phosphate metal salts such as zinc distearyl phosphate and barium dipalmityl phosphate, epoxy compounds such as bisphenol A diglycidyl ether and epoxidized soybean oil, triphenyl Chelators such as phosphite and isodecyl phenyl phosphite, lubricants such as methylene bis stearamide and ethylene bis stearamide, heat stabilizers such as barium stearate and calcium oleate, 2-hydroxy-4-octoxybenzophenone, etc. UV absorbers such as 2(2'-hydroxy-methylphenyl)benzotriazole, hindered amine light stabilizers, stabilizing aids such as dehydroacetic acid and dibenzoylmethane, 2,6-di-t-butyl-p-cresol, etc. anti-oxidants, antistatic agents such as polyoxyethylene/alkylamine, benzimidazole-based and phthalimide-based fungicides, algae-proofing agents, fluorine-based and silicone-based fog preventive agents, and colorants such as ultramarine blue.

The various additives mentioned above can be used alone or in combination of two or more. The amount of the various additives mentioned above is within a range that does not deteriorate the performance of the film, usually 5 parts by weight per 100 parts by weight of the base olefin resin.
You can choose within the range of parts by weight or less. To blend a fluorine-containing compound, a nonionic surfactant, a hindered amine compound, and various additives into the base polyolefin resin, weigh the necessary amounts of each and use a ribbon blender, Banbury mixer, super mixer, or other conventionally known method. You can use a blender or mixer that has a In order to form a film from the resin composition obtained in this way, methods known per se, such as melt extrusion molding method (including T-die method and inflation method), calender molding method, etc. It depends on the method.

[0020] Such a film may be a single layer, but it may also be a laminated film from the viewpoints of dustproofness, flexibility, and strength. The film according to the present invention may be transparent, satin finish, or semi-matte finish, and can be used for covering agricultural greenhouses (greenhouses), tunnels, etc., as well as for mulching, bagging, etc. Further, from the viewpoint of strength and cost, the film thickness is preferably in the range of 0.03 to 0.3 mm, more preferably 0.05 to 0.2 mm.

[0021]

Effects of the invention: The agricultural polyolefin resin film of the present invention provides appropriate bleed-out to the film surface, has excellent anti-fogging properties and anti-fogging durability at low temperatures, and also has excellent anti-fogging properties, and is free from whitening. It is suitable for agricultural covering materials because there is no reduction in transparency due to etc.

[0022]

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

Examples 1 to 15 Comparative Examples 1 to 7 As a three-layer inflation molding device, a three-layer die with a diameter of 100 mm (
(manufactured by Pura Koken Co., Ltd.), and the extruder has an outer and inner layer of 30 mm.
2 units of φ (manufactured by Pura Giken Co., Ltd.), the middle layer is 40 mmφ ((
(manufactured by Pura Giken Co., Ltd.), molding temperature 160℃, blow ratio 2
．． Table 2-1 of 0.1 mm thickness at a take-up speed of 5 m/min.
, 2-2 and 4-1 were obtained. The following evaluation tests were conducted on each of the obtained films. The results are shown in Tables 3-1, 3-2, and 4-2.

1) Transparency test The parallel light transmittance of the film obtained in the present invention at a wavelength of 555 millimicrons was measured using a spectrophotometer (manufactured by Hitachi, Ltd., 3
30 type), and the values are shown.

2) Low-temperature antifogging property Put 300cc of water (15°C) into a 500cc beaker, cover it with a sample film, and then place it in a constant temperature water bath (15°C).
Tilt the beaker 10 degrees from the ground surface and
The film surface was immersed in water up to part 3 and left in a constant temperature room at 0° C. for a predetermined period of time, and then the state of the film surface was observed with the naked eye. The flow state of water droplets on the film surface was evaluated using the following criteria. 〇: No part with drops (micro water droplets) ○ ×: Part with drops is 10% or less △: Part with drops is 30% or less ×: Part with drops exceeds 40%

3) Anti-fog durability Pour 300cc of water (45°C) into a 500cc beaker, cover with specimen film, and then place in a constant temperature water bath (45°C).
Tilt the beaker 10 degrees from the ground surface and
The condition of the film surface was observed with the naked eye after the film was immersed in water up to part 3 and left in a constant temperature room at 25° C. for a predetermined period of time. The flow state of water droplets on the film surface was evaluated using the same criteria as the low-temperature antifogging properties.

4) A pipe house (width 3 m, depth 5 m, ridge height 1.5 m) 22 in which the fog-proof test sample film was installed in a test field in Ichishi District, Mie Prefecture
Each ridge was coated. 5 days immediately after coating the pipe house (September 25th to September 30th, 1989), approximately 3 days after coating
5 days after the next month (December 22, 1989 to December 27, 1989)
days), 5 days after 5 months (from February 25, 1990 to March 1, 1990), and 5 days after 7 months (from April 15 to 4, 1990).
20th day of the month) After a certain period of time, the degree of fog generation was observed and evaluated with the naked eye. The evaluation criteria were as follows. 1...No fog is observed inside the house, or a slight amount of fog is generated only near the inner surface of the film. 2...There is fog throughout the house, but the back of the house can be clearly identified 15 meters away. 3...The whole house was covered in a rather thick fog, making it impossible to clearly discern the back of the house from 15 meters away. 4...The entire house was covered in fog, making it impossible to see the back of the house from 15 meters away.

5) A pipe house (width 3 m, depth 5 m, ridge height 1.5 m, roof slope 30 degrees) installed in a test field in Isshi District, Mie Prefecture was coated with a dust-proof sample film, and the pipe house was used from September 1989 to 1990. Expansion tests were conducted for 12 months until September 2017. The film after the test was collected, and the parallel light transmittance at a wavelength of 555 mm was measured using a spectrophotometer (manufactured by Hitachi, Model 330). The standards for the measurement results were as follows. ◎: Light transmittance is 75% or more. ○: Light transmittance in the range of 65 to 74%. ○×: Light transmittance in the range of 55 to 64%. Δ: Light transmittance in the range of 40 to 54%. ×: Light transmittance less than 40%.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

[Table 6]

[0035]

[Table 7]

Claims (1)

[Claims] 1. 0.01 to 2 parts by weight of a fluorine-containing compound per 100 parts by weight of the polyolefin resin;
5 to 5 parts by weight of a nonionic surfactant, and 0.05 to 5 parts by weight of a nonionic surfactant.
An agricultural polyolefin resin film characterized by being blended with part by weight of a hindered amine compound.