JPH0195146A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PURPOSE:To obtain the title film having excellent (persistent) fog resistance at low temp. and water condensing property, by compounding a vinyl chloride resin, a specified mixture and a polyfluoroalkyl compd. and making a film thereof. CONSTITUTION:A mixture (B) is obtd. by mixing a compd. (a) prepd. by adding 1-30mol of alkylene oxide, pref. ethylene oxide and/or propylene oxide, to a nonylphenol-formaline condensate and a sorbitan ester (b), pref. sorbitan stearate and/or sorbitan palmitate with a ratio of 1-5/9-5. 100pts.wt. vinyl chloride resin (A) obtd. by (co) polymerizing vinyl chloride and, if necessary, vinylidene chloride, ethylene, propylene, etc., 0.5-4pts.wt. component B and 0.01-2pts.wt. 3-20C polyfluoroalkyl compd.(C) [e.g., a compd. of the formula (wherein Rf is 3-20C polyfluoroalkyl; B is -CO-, -SO2-)] are compounded together and the mixture is formed into a film to obtain the title film whose thickness is 0.03-0.3mm.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides an agricultural vinyl chloride resin film, which has excellent anti-fogging properties and anti-fogging durability especially at low temperatures, and also has excellent water aggregation ability. This invention relates to an agricultural vinyl chloride resin film that prevents moisture buildup.

[Prior Art] In recent years, greenhouse horticulture has been on the rise due to the ability to increase profits through forced cultivation or controlled cultivation of useful plants.

The covering materials used in this 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 film containing a large amount of plasticizer is widely used because it has superior light transmittance, heat retention, mechanical strength, and weather resistance compared to other synthetic resin films. .

By the way, since the vinyl chloride resin film has a hydrophobic surface, when it is spread on the house, water vapor generated inside the house becomes water droplets and condenses on the inner surface of the film. Therefore, the condensed water droplets not only significantly reduce light transmission and block sunlight from irradiating the cultivated crops, but also fall onto the cultivated crops and may cause damage to the crops.

Furthermore, since the condensation of moisture inside the greenhouse relies solely on the effect of the antifogging agent, the interior of the greenhouse tends to become humid, and in some cases there is a risk of disease.

Conventionally, in order to solve this problem, vinyl chloride resin is made hydrophilic so that the water droplets condensing on the surface flow down while uniformly wetting, and in order to prevent fogging due to dew condensation on the inner surface of the film, it is necessary to add hydrophilicity to the vinyl chloride resin before forming the film. Antifogging agents have been incorporated into vinyl chloride resin compositions.

Antifogging agents generally include sorbitan surfactants such as sorbitan monostearate, sorbitan monopalmitate, and sorbitan monobenzoate, and glycerin surfactants such as glycerin monolaurate, diglycerin monopalmitate, and glycerin monostearate. agent,
Polyethylene glycol-based surfactants such as polyethylene glycol monostearate and polyethylene glycol monopalmitate, esters of condensates of sorbitan and glycerin, and organic acids are known, and these surfactants can be used alone or in combination. Two or more types are used in combination.

However, although such antifogging agents used for boat fishing have normal antifogging properties at low temperatures, they have insufficient antifogging properties at low temperatures when used in regions with severe winter temperatures.

In order to further improve hydrophilicity and speed up the run-off time of condensed water, surfactants with alkylene oxide, especially ethylene oxide added to the above surfactants are often used to address these problems, but performance improvements at low temperatures are still insufficient. Moreover, since the hydrophilicity is improved, the long-lasting effect as an antifogging agent is reduced.

To deal with this, it is possible to have a lasting effect by increasing the amount of antifogging agent added, but if a large amount of antifogging agent is used, the antifogging agent will bleed over time and the film will become sticky. Furthermore, there was a problem that the film itself became white.

Therefore, the technology to improve the concentration of moisture in the greenhouse still remains an issue.

Based on the above, a film that has the three properties required for maintaining a good greenhouse environment: anti-fogging properties at low temperatures, anti-fogging durability, and moisture aggregation ability has not yet been found. do not have.

[Problem that the invention seeks to solve]

An object of the present invention is to provide an agricultural vinyl chloride resin film that has excellent antifogging properties and durability at low temperatures, and also has excellent water aggregation ability and prevents humidity in greenhouses.

Means for Solving Problem C] In order to achieve the above object, the present inventors have made extensive studies,
By using a combination of an alkylene oxide adduct of a nonylphenol/formalin condensate and a sorbitan ester, as well as a compound having a polyfluoroalkyl group having 3 to 20 carbon atoms, excellent low-temperature anti-fogging properties and long-lasting anti-fogging effects can be achieved. It was discovered that an agricultural vinyl chloride resin film having a water coagulation effect can be obtained, and the present invention was achieved.

That is, in the present invention, for 100 parts by weight of vinyl chloride resin,
A mixture of sorbitan ester and a compound obtained by adding 1 to 30 moles of alkylene oxide to a nonylphenol/formalin condensate and 0.5 to 4 parts by weight and 3 to 20 carbon atoms
Compounds having a polyfluoroalkyl group of 0.01 to 2
This is an agricultural vinyl chloride resin film characterized by containing part by weight.

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

In the present invention, a mixture of an alkylene oxide adduct of a nonylphenol/formalin condensate and a sorbitan ester is used.

The nonylphenol/formalin condensate, which is the raw material for the compound in which an alkylene oxide is added to the nonylphenol/formalin condensate, which is the active ingredient of the present invention, can be prepared using known techniques such as mixing nonylphenol and formalin in a solvent in the presence of an acid or alkali catalyst. It is obtained by condensation by heating below.

The degree of condensation is preferably 2 to 10, particularly 3 to 7.
Particularly preferred from the viewpoint of long-lasting antifogging performance. Note that the degree of condensation corresponds to the number of nonylphenols in one condensate.

Furthermore, the alkylene oxide adduct of a nonylphenol/formalin condensate is one in which ethylene oxide and/or propylene oxide is added to the formalin condensate.

The addition of alkylene oxide to the nonylphenol-formalin condensate is carried out using a known technique, for example, by reacting the condensate with alkylene oxide under heating in the presence of an alkali catalyst.

The addition rate of alkylene oxide is preferably 1 to 30 moles when only ethylene oxide is added. In particular, when the addition rate is 1 to 15 moles, the antifogging effect is long-lasting.

The effective antifogging agent composition in the present invention includes alkylene oxides 1 to 3 of the above nonylphenol/formalin condensate.
It is a mixture of 0 molar adduct and sorbitan ester.

As the sorbitan ester, sorbitan stearate or sorbitan palmitate is preferred. Esters of fatty acids with less than 15 carbon atoms have a good initial effect but lack sustainability, while esters of fatty acids with a prime number of more than 19 have good sustainability but have poor initial effects.

The mixing ratio of the alkylene oxide adduct of the above nonylphenol formalin condensate and sorbitan ester is 1
/9 to 515 is preferable, more preferably 2/8 to 4/
It is 6. If it is smaller than 1/9, the initial effect will be inferior, and if it is larger than 515, the sustained effect will be inferior.

The amount of the antifogging agent mixture added is preferably 0.5 to 4 parts by weight, more preferably 1 to 3 parts by weight, per 100 parts by weight of the vinyl chloride resin. If the amount added is less than 0.5 part by weight, the antifogging performance will be poor, which is not preferable. On the other hand, if the amount is more than 4 parts by weight, the film tends to become sticky or white due to bleeding, resulting in a decrease in commercial value.

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

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

(1) RfBF In this formula, Rt represents a polyfluoroalkyl group having 3 to 20 carbon atoms, and B represents -〇〇-1-SO,-.

These R, and B have the same meaning in the following general formula.

(21R,0H (3) R1BNmoR'O+THZ In this formula, R1 represents -C, H, -2Cs H6-,
R2 represents a hydrogen atom or a lower alkyl group, and n is 1 to 3
Represents an integer of 0. Moreover, these R1 and R2 have the same meaning in the following general formula.

(4) H-(CHCH1←rR” C00CHt Rt In this formula, a represents an integer from 1 to 100.

(5) H+CH-CH, →T→CH-CH, -)-r
R"I C0OCH, R, COO+R' O+T-H In this formula,
b represents an integer of 1 to 40, C represents an integer of 1 to 100, b
and C have the same meanings in the following general formulas.

(6) H+CH, CRL) TS CH, WCH, S+C
HICR3-h-Hll CQ Rr C=O0X In this formula, R3 represents a hydrogen atom or a methyl group, Q represents a bifunctional organic group, and W represents -C00- or -CH,O-. R3, Q and W have the same meanings in the following general formulas.

(7) H-(CH,CRgoh S CHz W+
CHx CHOh R”C-Q-R,Rg II (8) R, C00M In this formula, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, N Ha 0M represents “” also in the following general formula. have similar meanings.

(9) R,BNR'C00M Rt 0ω R,SO,M 01) Rf CH! QC, HX, 503M In this formula, m represents an integer of 1 to 20. 0m has the same meaning in the following general formula.

02)　MO,5CHCOOCH,R.

CH, C00CH, Rf Ori Rf BNC, HX, OP (OM)! l
II R”0 04) Rt B N CtH4N R% -H
Xz In this formula, HX represents halogen acid.

(15) R, BNC, H, N"R3"-X-■ i In this formula, X represents a halogen acid group. The following 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. - For boat fishing, the amount is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight per 100 parts by weight of vinyl chloride resin.

If it is less than 0.01 part by weight, the effect of water aggregation ability will be poor, and if it is more than 2 parts by weight, the film will tend to become cloudy.

The film according to the present invention may contain other resin additives, if necessary.
For example, plasticizers, lubricants, heat stabilizers, antioxidants, ultraviolet absorbers, pigments, dyes, etc. can be added.

As a plasticizer, for example, Zyrow octyl phthalate,
Phthalic acid derivatives such as di2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diisodecyl phthalate, isophthalic acid derivatives such as diisooctyl isophthalate, adipic acid derivatives such as dibutyl adipate, dioctyl adipate, Maleic acid derivatives such as dibutyl maleate, citric acid derivatives such as tri-n-butyl citrate, itaconic acid derivatives such as monobutyl itaconate, oleic acid derivatives such as butyl oleate, ricinoleic acid derivatives such as glycerin monolysylate, etc. can be given.

The above plasticizers may be used alone or in combination of two or more, and 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.
1-10 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, epoxidized methyl stearate, epoxidized butyl stearate,
Epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate and other esters, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil fatty acid butyl, 3-(2-xenoxy) -1,2-Epoxypropane, bisphenol A diglycidyl ether, vinylcyclohexene jepoxide, dicyclopentene diepoxide, 3,4-epoxy-6-methylcyclohexylmethyl, 314-epoxy-6-methylcyclohexanecarboxylate, etc. It will be done.

The appropriate amount of these epoxy compounds to be used is usually 0.5 to 7 parts by weight per 100 parts by weight of the vinyl chloride resin.

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.

Examples of the ultraviolet absorber include hydroquinone-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers.

The basic vinyl chloride resin composition is vinyl chloride +
A mixture of an alkylene oxide adduct of nonylphenol/formalin condensate and sorbitan ester, a compound having a polyfluoroalkyl group having 3 to 20 carbon atoms, and other resin additives are blended with jA fat, and a ribbon blender, a Banbury mixer, etc. -, obtained by mixing with a super mixer, Henschel mixer, etc.

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

If the thickness of the film according to the present invention is too thin, the strength will be insufficient, so it is undesirable. On the other hand, if it is too thick, it will not be suitable for film processing or other handling (cutting the film and joining it into a house shape, etc.) Usually 0.03 to 0.3+
ms, preferably 0.05 to 0.21.

Furthermore, the film of the present invention may have its surface coated with a resin such as acrylate resin or polyvinylidene fluoride in order to impart dustproof properties.

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

Examples 1 to 6, Comparative Examples 1 to 7 Antifogging agents and fluorine compounds of the types and amounts shown in Table 2 were added to the basic formulation shown in Table 1 below, mixed for 10 minutes with a Henschel mixer, and heated at 165°C. An agricultural vinyl chloride resin film (hereinafter abbreviated as agricultural vinyl) having a thickness of 0.10+ m was obtained using a roll-kneaded roll calender.

Table-1 Basic composition The following evaluation tests were conducted on the obtained agricultural vinyl.

The results are shown in Table-2.

Measurement method (1) Anti-fogging properties at low temperatures After each film was set in a wooden frame whose top surface had an inclination of 10°, it was placed in a low-temperature bath filled with 20°C water and kept at an external temperature of O'C. I put the frame in and submerged it to a depth of 1/4 from the water surface.

Thereafter, the state of water condensation 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 the condensed water droplets started flowing along the film was also observed.

(2) Anti-fogging persistence After each film was set in a cylinder with an inner diameter of 8 CI11 and a height of 10 cm, it was placed in a constant temperature water bath kept at a water temperature of 40°C so that the inclination was 5°.

The state of condensation of water droplets was observed over time, and sustainability was determined based on the number of days during which 1/2 of the film area lost its antifogging properties.

(3) Moisture aggregation ability The films of Examples 1 to 3 and Comparative Examples 1.2 and 7 were glued together in a strip shape with a length of 6 m and a width of 1.5 m, and films other than those tested were provided at both ends.1. A rain gutter with partitions every 5 m was installed on the ceiling of a pipe house with a width of 4 m and a length of 10 m, which was attached to the shoulder.

Thereafter, a fixed amount of water was sprinkled into the pipe house twice a day at 9:00 and 17:00, and water flowing down the inner surface of the film was collected and the amount of water was measured to evaluate the water aggregation ability.

The measurement was carried out for 10 days and calculated as the average value of the amount of water flowing down per hour on the inner surface of the film (1rI).The unit is g/bo·hr.

(4) Fog-proof properties After placing each film in a small test house (semi-cylindrical shape) with a width of 40 cm, a height of 35 cm, and a length of 50 cm + n, place the film in a constant-temperature water tank with the water temperature kept at 35°C, at the height of the house from the water surface. It sank until it reached a depth of 27 cm.

Thereafter, a cloth cooled to 5°C was covered over the film, and the state of fog generated from the inner surface of the film was observed from the end.

○: No fog generation is observed.

Δ: Slight occurrence of fog is observed.

×: Heavy fog generation.

(5) Surface condition of film Each film was left in a constant temperature and humidity chamber at 50°C x 65%, and after a predetermined period of time, it was taken out and the state of embossment on the film surface was visually determined.

O: No embossment.

△: It is raised, but there is little stickiness.

×: Severe lifting and significant stickiness.

[Effects of the Invention] As is clear from the above examples, the film of the present invention, which uses the antifogging agent and fluorine compound of the present invention in combination, has a lower temperature than the film that uses the conventional antifogging agent and fluorine compound in combination. It has good antifogging effect (flow start time, surface condition B) and durability, and is also excellent in water aggregation effect.

On the other hand, when a fluorine compound is not used in combination, a large difference in water aggregation ability is observed, resulting in poor fog-proofing properties.

When the amount of the antifogging agent of the present invention added exceeds 4 parts by weight, low-temperature antifogging properties, surface condition, and durability are good, but a blowout phenomenon tends to occur.

Further, when the amount of the antifogging agent of the present invention added is less than 0.5 parts by weight, the antifogging performance is poor.

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

■It has good anti-fog properties at low temperatures, so it can provide sufficient anti-fog effects even in extremely cold regions.

■Because it has a high water coagulation ability, it can prevent the inside of the greenhouse from becoming too humid, and it can also reduce the occurrence of diseases that occur in crops in humid environments.

■Since it has a good anti-fog effect, it can ensure sufficient light even in the winter when there are few hours of sunlight, creating a favorable environment for crop cultivation.

■Since it has good sustainability, it can prevent water droplets from falling over a long period of time, and it can also ensure a sufficient amount of light until the crop is harvested, so it can be expected to improve the quality and yield of crops.

■The condition of the inner surface is good, so you can get a uniform light beam,
It also makes it easier to observe the inside of the house from outside.

Claims (1)

[Claims] 1. 100 parts by weight of vinyl chloride resin, 1 part alkylene oxide in nonylphenol formalin condensate
It is characterized by containing 0.5 to 4 parts by weight of a mixture of a compound added with ~30 moles and a sorbitan ester, and 0.01 to 2 parts by weight of a compound having a polyfluoroalkyl group having 3 to 20 carbon atoms. Agricultural vinyl chloride resin film. 2. The agricultural vinyl chloride resin film according to claim 1, wherein the alkylene oxide is ethylene oxide and/or propylene oxide. 3. The agricultural vinyl chloride resin film according to claim 1, wherein the sorbitan ester is sorbitan stearate and/or sorbitan palmitate. 4. The mixing ratio of alkylene oxide adduct of nonylphenol/formalin condensate and sorbitan ester is 1.
1. The agricultural vinyl chloride resin film according to claim 1, which has a particle size of /9 to 5/5.