JPH1180477A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural vinyl chloride resin film which can retain its drip-proof and antifogging properties for a long term without exhibiting the degradation in these properties at the early stage by compounding a vinyl chloride resin with composite metal hydroxide salt particles, inorg. particles selected from among silica, magnesium hydroxide, aluminum hydroxide and feldspar and a drip-proof agent, each in a specified amt. SOLUTION: This film is prepd. from a compsn. prepd. by compounding 100 pts.wt. vinyl chloride resin (e.g. PVC) at least with 0.1-15 pts.wt. particles of a composite metal hydroxide salt of formula I (wherein Y is an n-valent anion; M is a divalent metal; 0.01<=x<1: and 0<=m)(e.g. a salt of formula II), 0.1-5 pts.wt. inorg. particles selected from among silica, magnesium hydroxide, aluminum hydroxide and feldspar and a drip-proof agent (pref. a sorbitan-based one) pref. in an amt. of 0.3-5 pts.wt. Pref., 0.001-0.3 pt.wt. β-diketone compd. (e.g. dibenzoylmethane) is incorporated into the compsn. to prevent the discoloration.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin film used as an agricultural covering material.

[0002]

2. Description of the Related Art Conventionally, as a covering material (agricultural covering material) used for agricultural facilities such as tunnels and agricultural houses,
It is made of vinyl chloride resin such as polyvinyl chloride, which is a homopolymer of vinyl chloride, because it is inexpensive, has good transparency, is excellent in heat retention and strength, and is easy to be formed into a film (has good workability). Film is widely used. This agricultural film made of polyvinyl chloride or the like (agricultural vinyl chloride resin film) is generally obtained by adding a plasticizer, a stabilizer, a drip-proof agent, an anti-fog agent to a vinyl chloride resin such as polyvinyl chloride.
The composition obtained by adding a predetermined amount of an additive such as an ultraviolet absorber is formed into a film by a method such as a calendar method.

[0003]

In recent years, however, there has been a demand for agricultural covering materials that can be spread over a long period of time because of the labor shortage of farmers and resource saving. Many proposals have been made for long-term expansion. In particular, in order for agricultural PVC films to be stretchable over a long period of time, it is essential to maintain drip-proof and fog-proof properties over a long period of time. Many proposals have been made that specify the use of other additives in combination.

However, when the drip-proof property and the fog-proof property are maintained for a long period of time, the initial drip-proof property and the fog-proof property generally tend to decrease. The present invention has been made in order to solve the above-mentioned problems, and is capable of maintaining drip-proof and fog-proof properties for a long time without lowering the initial drip-proof and fog-proof properties. It is an object to provide a vinyl resin film.

[0005]

Means for Solving the Problems The agricultural vinyl chloride resin film of the present invention made in order to solve the above-mentioned problems is characterized in that at least a drip-proof agent and inorganic particles are added to a vinyl chloride resin. An agricultural vinyl chloride-based resin film obtained by forming a vinyl-based resin composition into a film,
The inorganic particles are 0.1 to 15 parts by weight per 100 parts by weight of the vinyl chloride resin.
It is characterized by containing one or more inorganic particles selected from silica, magnesium hydroxide, aluminum hydroxide and feldspar in parts by weight.

Embedded image

In the present invention, the term "vinyl chloride resin" refers to polyvinyl chloride, which is a homopolymer of vinyl chloride, as well as polyvinyl chloride, ethylene and propylene, as in the case of the conventional vinyl chloride resin for agricultural vinyl chloride resin film. Copolymers with vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, acrylates, methacrylates, maleic acid, fumaric acid, acrylonitrile, alkyl vinyl ethers, etc., mixtures of these resins, these resins and other It is a mixture with a resin.

Various additives such as a plasticizer, a stabilizer, a lubricant or an anti-adhesion agent, an ultraviolet absorber, an antifog agent, an antioxidant, and a light stabilizer are added to the vinyl chloride resin as required. Is added.

Specific examples of the plasticizer include di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dilauryl phthalate, didecyl phthalate, diundecyl phthalate, and ditridecyl phthalate. Phthalate plasticizers such as tricresyl phosphate, trixylyl phosphate, tris (isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phenyl phosphate, etc. Phosphate plasticizers such as dioctyl adipate; Adipate ester plasticizers such as ditrinonyl adipate and diisodecyl adipate; polyester plasticizers; sebacate ester plasticizers; Epoxy plasticizers epoxidized soybean oil, and the like; trimellitic ester plasticizer least one selected from the like can be used. The amount of the plasticizer is about 30 to 70 parts by weight per 100 parts by weight of the vinyl chloride resin.

As the stabilizer, a commonly used stabilizer such as a metal soap and an organic phosphite stabilizer can be used. As metal soaps, zinc stearate,
Examples include barium stearate, calcium stearate, barium ricinoleate, calcium laurate, calcium oleate, zinc octoate, and the like. Examples of the organic phosphite-based stabilizer include diphenyldecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tristearyl phosphite, and octyl diphenyl phosphite. And the like. The above stabilizers can be used alone or in combination of two or more.

Examples of the lubricant or anti-adhesive include fatty acid lubricants such as stearic acid, isostearic acid and palmitic acid; fatty acid amide lubricants such as stearic acid amide, methylenebisstearamide and ethylenebisstearamide; butyl palmitate Butyl stearate and the like; lubricants such as metal salts of organic phosphates such as barium isodecyl phosphate and calcium octadecyl phosphate; polyethylene wax and liquid paraffin. The above lubricants or antiadhesives can be used alone or in combination of two or more.

As the ultraviolet absorber, generally used ultraviolet absorbers such as benzophenone type, benzotriazole type, salicylate type and cyanoacrylate type can be used. The above-mentioned ultraviolet absorbers can be used alone or in combination of two or more.

Specifically, fluorine-containing compounds conventionally used as an antifog agent for agricultural films can be used as the antifog agent. This fluorine-containing compound is a compound having a fluorine-containing group and at least one of a hydroxyl group and an alkylene oxide group in one molecule. As the fluorinated group, a perfluoroalkyl group [C _n F
_{2n + 1} -], perfluoroalkoxy group [C _n F _{2n + 1} O
-], polyfluoroalkyl group [H _m C _n F
_{2n + 1-m} −], a perfluoroalkenyl group [C _n F
_2n-1 -], polyfluoroalkenyl group [H _m C _n F
_2n-1-m -], perfluoroalkylene group [C _n F _2n -]
(Where m is 1 to 3 and n is 3 to 20)
), And the alkylene oxide group includes [-(C
₂ H ₄ O) _n -], _{[- (C 3 H 6 O)} n - ] and the like (provided that n is 1 to 30 integer).

Specifically, the above-mentioned fluorine-containing compound includes:
Examples include those shown in (1) to (13) of Chemical Formula 3, but are not limited thereto.

Embedded image

The amount of the above antifoggant is about 0.01 to 1.0 part by weight based on 100 parts by weight of the vinyl chloride resin.
Particularly preferably, it is about 0.05 to 0.5 part by weight.
If the added amount of the anti-fog agent is too small, the film obtained will have insufficient fog resistance, and if the added amount of the anti-fog agent is too large, the cost will increase.

As the light stabilizer, a hindered amine light stabilizer having a 2,2,6,6-tetramethylpiperidine unit, which is generally used, can be used. The hindered amine light stabilizer preferably has a molecular weight of about 800 to 2,000. The amount of the light stabilizer is about 0.01 to 0.3 parts by weight based on 100 parts by weight of the vinyl chloride resin.

The vinyl chloride resin composition constituting the agricultural vinyl chloride resin film of the present invention further improves the weather resistance of the obtained film in addition to the above-mentioned commonly used additives. For this purpose, an organic phosphorus compound shown in Chemical formula 4 can be added.

Embedded image

The vinyl chloride resin composition constituting the agricultural vinyl chloride resin film of the present invention contains a drip-proof agent. As this drip-proofing agent, any one can be used as long as it is conventionally used.
Particularly preferred is a sorbitan dripproofing agent.

Specific examples of the sorbitan dripproofing agent include:
Sorbitan palmitate, sorbitan stearate, sorbitan stearate / ethylene oxide 1 mol adduct, sorbitan stearate / ethylene oxide 2 mol adduct, sorbitan stearate / propylene oxide 3 mol adduct, sorbitan stearate adipate / ethylene oxide 3 mol Additives can be used.

Specific examples of the above-mentioned non-sorbitan-based dripproofing agents include diglycerin stearate, sorbitol stearate, sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmitate / ethylene oxide 2 mol addition Sorbitol stearate adipate / ethylene oxide 2 mol adduct, diglycerin palmitate sebacate / propylene oxide 3 mol adduct, sorbitol palmitate adipate / ethylene oxide 3 mol adduct and the like can be used.

The amount of the above drip-proofing agent is 0.3 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the addition amount of the drip-proof agent is too small, the drip-proof property of the obtained film is insufficient, and if the addition amount of the drip-proof agent is too large,
In addition to the increase in cost, there is a concern that the added drip-proofing agent blooms and impairs the transparency of the obtained film.

The vinyl chloride resin composition constituting the agricultural vinyl chloride resin film of the present invention comprises, together with a drip-proof agent, composite metal hydroxide salt particles represented by the above formula (2), silica, magnesium hydroxide and water. It contains one or more inorganic particles selected from aluminum oxide and feldspar.

The complex metal hydroxide salt shown in Chemical formula 2 is a complex metal hydroxide salt containing ions of lithium (Li), aluminum (Al) and one or more divalent metals (M). . Specific examples of the divalent metal include one or more selected from magnesium (Mg), zinc (Zn), barium (Ba), calcium (Ca), cadmium (Cd), lead (Pb), and the like. Is preferably magnesium or / and zinc.

Y in the formula shown in Chemical Formula 2 is an n-valent anion. Specific examples of the Y include carbonate ion, perchlorate ion, phosphate ion, phosphite ion, metaphosphate ion, acetate ion, propionate ion, adipate ion, benzoate ion, phthalate ion, terephthalate acid. Ion, maleate ion, fumarate ion, citrate ion, tartrate ion, succinate ion, p-oxybenzoate ion, salicylate ion, picrate ion,
Examples thereof include silicate ions, sulfate ions, nitrate ions, iodine ions, fluorine ions, chlorine ions, and bromine ions.

As the composite metal hydroxide salt particles shown in Chemical formula 2, particles having an average particle diameter of 0.01 to 10 μm are preferable, and particles having a plate-like shape are preferable.
The composite metal hydroxide salt particles may be those in which secondary particles are formed, and in the case where secondary particles are formed, the average particle diameter is the average particle diameter of the secondary particles. Refers to the diameter. Further, as the composite metal hydroxide salt particles, those having a refractive index of about 1.45 to 1.55 are particularly suitable. Further, the composite metal hydroxide salt particles, in order to improve the dispersibility in the vinyl chloride resin composition,
It may be surface-treated with a surface treatment agent such as paraffin, higher fatty acid, alkali metal salt of higher fatty acid, higher alcohol, polyhydric alcohol, and coupling agent.

The amount of the composite metal hydroxide salt particles shown in Chemical formula 2 is 0.1 to 100 parts by weight of the vinyl chloride resin.
15 parts by weight, particularly preferably 1 to 10 parts by weight.
If the added amount of the composite metal hydroxide salt particles is too small,
If the drip-proof durability is not sufficiently improved, and if the addition amount is too large, there is a concern that the transparency and strength of the obtained film are reduced.

From the silica, magnesium hydroxide, aluminum hydroxide, and feldspar added to the vinyl chloride resin composition constituting the agricultural vinyl chloride resin film of the present invention together with the above composite metal hydroxide salt particles. The selected one or more inorganic particles have an average particle size of 0.01 to 20.
μm is preferred.

The amount of the inorganic particles to be added is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. The ratio of the composite metal hydroxide salt particles and the inorganic particles such as silica added to the vinyl chloride resin composition is 1: 1 to 10: 1.
It is desirable to be about. Even if inorganic particles such as silica are added in an amount equal to or greater than the amount of the composite metal hydroxide salt particles, the drip-proof durability is not further improved, but rather the transparency and strength of the obtained film are improved. On the other hand, even if inorganic particles such as silica are added in an extremely small amount less than one-tenth of the amount of the composite metal hydroxide salt particles, the composite metal hydroxide There is no particular difference from the case where the salt particles are added alone.

The agricultural vinyl chloride resin film comprising the vinyl chloride resin composition to which the composite metal hydroxide salt particles have been added contains, in this vinyl chloride resin composition,
Even if none of silica, magnesium hydroxide, aluminum hydroxide, and feldspar are added, the drip-proof durability is improved. However, the present invention relates to the composite metal hydroxide salt particles, silica, By adding together one or more inorganic particles selected from magnesium, aluminum hydroxide and feldspar, it is found that the drip-proof durability is improved as compared with the case where the composite metal hydroxide salt particles are added alone. As a result, it was completed.

When the above-mentioned composite metal hydroxide salt particles are added to a vinyl chloride resin composition, the composition tends to be discolored when it is formed into a film by calendering or the like. To prevent this, it is desirable to add a β-diketone compound in addition to the above. As this β-diketone compound, dibenzoylmethane, methoxybenzoyl benzoylmethane, chlorobenzoyl benzoylmethane, palmitic benzoylmethane and the like can be used.

The amount of the β-diketone compound is from 0.001 to 0.3 based on 100 parts by weight of the vinyl chloride resin.
It is about parts by weight. If the addition amount of the β-diketone compound is too small, the above-mentioned effects are not sufficiently exhibited, and even if the β-diketone compound is added in excess of the above addition amount, the cost is merely increased.

When the above-mentioned inorganic particles are added to a vinyl chloride resin composition, the weather resistance of the resulting film tends to decrease. In order to suppress this, it is desirable that the light transmittance at a wavelength of 330 nm be suppressed to 50% or less by selecting and adjusting the type and the amount of the ultraviolet absorber. However, if the light transmittance of the ultraviolet band is suppressed more than necessary, there is a concern that adverse effects such as coloring of the crop may be caused, and in consideration of the characteristics of the crop cultivated using the same, It is important to determine the light transmittance in the ultraviolet band. Of course, 33
The light transmittance at a wavelength of 0 nm is 50% or less, and a phosphoric acid ester plasticizer such as trixylyl phosphate for improving the weather resistance of the film, or an organic phosphorus compound or a hindered amine compound represented by Chemical Formula 4 above. It is necessary to improve the weather resistance of the obtained film by adding a stabilizer or the like in order to obtain an agricultural film that can be extended for a long time.

The above-mentioned vinyl chloride resin composition is formed into a film by known means such as a calendering method, an extrusion method and an inflation method, and the vinyl chloride resin film of the present invention is obtained. The processing conditions such as the temperature at the time of forming the film need not be particularly changed from those of the conventional agricultural vinyl chloride resin film.

The vinyl chloride resin film for agriculture of the present invention obtained as described above is coated with a solvent-based or water-based resin on the outer surface when expanded, like a conventional vinyl chloride-based resin film for agriculture. Alternatively, a dust-proof coating film formed by applying a UV-curable coating material may be provided. As the solvent-based paint, for example, an acrylic resin-based, vinyl chloride resin-based, cellulose resin-based, fluorine resin-based, polyamide resin-based, urethane resin-based, epoxy resin-based, or silicone resin-based paint can be used. As the water-based paint, for example, an acrylic resin-based, polyester resin-based, urethane resin-based, epoxy resin-based paint, or the like can be used. Examples of UV-curable paints include acrylic resin, acrylic-modified urethane resin, acrylic-modified epoxy resin,
A paint such as a mercapto derivative or an epoxy resin can be used.

Further, the vinyl chloride resin film for agricultural use of the present invention is a film for imparting drip-proof property to a surface which becomes inside when stretched, for example, the above-mentioned solvent-based, water-based or ultraviolet-ray-coated film. A coating film formed by applying a coating material obtained by adding colloidal silica or the like to a curable coating material may be formed.

[0035]

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples shown below.

Examples 1 to 6, Comparative Examples 1 to 3 A vinyl chloride resin composition having the composition shown in Table 1 was applied to a film having a thickness of 0.1 mm using a calender at a roll temperature of 180 ° C. It was molded to obtain a vinyl chloride resin film.
The obtained vinyl chloride resin film was applied to a width of 1 m and a height of 8 m.
It was spread on a tunnel house having a length of 0 cm and a length of 10 m, and the initial drip-proof property and drip-proof durability were evaluated by the following methods. Table 1 shows the results.

(1) Initial Drip-Proof Property Three days after the spreading, the state of the film on the inner surface side of the house was visually observed and evaluated according to the following criteria. [Criterion] 5: Water droplets are not seen at all, and water is flowing in a film form. 4: Water droplets can be seen very slightly, but water flows in a film form and flows neatly. 3: There are few water drops, but there are many places where water flows in a streak shape. 2: There are many water droplets, and the water flows in a streak shape. 1: A large amount of water droplets adhered and hardly flowed. (2) Drip-proof durability Three months, six months, and 12 months after the spreading, the state of the film on the inner surface side of the house was visually observed and evaluated based on the same criteria as described above.

[0038]

[Table 1]

[0039]

As described above, the vinyl chloride resin film for agriculture of the present invention has an initial drip-proof property due to a composition added in combination with a specific composite metal hydroxide salt and an inorganic powder. Not only that, the effect is maintained, but also the sustainability of the effect is remarkably improved.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/34 C08K 3/34 3/36 3/36 5/07 5/07 5/15 5/15

Claims (5)

[Claims] An agricultural vinyl chloride resin film comprising a vinyl chloride resin composition obtained by adding at least a drip-proofing agent and inorganic particles to a vinyl chloride resin, wherein the inorganic particles are made of chloride. 0.1 to 15 parts by weight of the composite metal hydroxide salt particles shown in Chemical Formula 1 per 100 parts by weight of the vinyl resin, and 0.1 to 5 parts by weight of silica and magnesium hydroxide per 100 parts by weight of the vinyl chloride resin, A vinyl chloride resin film for agricultural use, comprising one or more inorganic particles selected from aluminum hydroxide and feldspar. Embedded image 2. The composite metal hydroxide salt particles shown in Chemical Formula 1 have an average particle size of 0.01 to 10 μm, and an average of one or more inorganic particles selected from silica, magnesium hydroxide, aluminum hydroxide, and feldspar. Particle size is 0.01-20μ
2. The agricultural polyvinyl chloride resin film according to claim 1, wherein m is m. 3. The agricultural polyvinyl chloride resin film according to claim 1, wherein the composite metal hydroxide salt particles shown in Chemical formula 1 are plate-like particles. 4. The agricultural polyvinyl chloride resin film according to claim 1, wherein the drip-proof agent is a sorbitan-based drip-proof agent. 5. Agriculture according to claim 1, wherein the vinyl chloride resin composition contains 0.001 to 0.3 parts by weight of the β-diketone compound per 100 parts by weight of the vinyl chloride resin. Vinyl chloride resin film.