JPS6227146A - Agricultural flexible vinyl chloride group resin film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Field of Application - 1 The present invention provides dustproof properties, weather resistance, heat retention, glazing strength, anti-fog durability, house WJ adhesion, persistence of transparency, spreading workability, This product relates to a flexible vinyl chloride resin film for agricultural use that is particularly economical and has excellent long-lasting transparency and ease of handling without reducing opening/closing workability during ventilation or soil hardening properties. be.

"Prior Art" In recent years, farmers have widely adopted methods of promoting cultivation of useful plants in agricultural greenhouses or tunnels in order to increase profitability. As covering materials for agricultural greenhouses, tunnel houses, etc., soft vinyl chloride films (fat films, polyethylene films, polyethylene terephthalate films, etc.) are used. Compared to synthetic resin films, it is easier to mix various additives, so weather resistance and
It has excellent anti-fog properties, heat retention, transparency, toughness, and durability. In addition, since the soft vinyl chloride resin film is soft and elastic, it has been widely used because it can be stretched into any shape of house or tunnel.

However, since soft vinyl chloride resin films contain large amounts of plasticizers, antifogging agents, and various other additives, these plasticizers and other additives may ooze out onto the film surface during use, resulting in Dust adheres to the film surface, which reduces light transmittance, adversely affects weather resistance, and makes the film sticky during adhesion, stretching, and ventilation, making it difficult to handle.

Also, two summers since the start of film expansion (the second summer)
As time passes, the "anti-fogging" property of allowing condensed water adhering to the inner surface to flow down along the inner surface of the film without allowing it to fall onto the cultivated crops decreases, causing a decrease in light transmittance or causing condensed water on the cultivated crops to flow down. They may fall on plants and cause disease outbreaks or pollination problems.

On the other hand, polyethylene (PE) film is superior to soft vinyl chloride I5 in terms of price, availability of raw materials, ease of spreading, and dust resistance.
Although it has an advantage over (PVC) film in terms of workability, its range of use is severely restricted due to its inferior antifogging properties, heat retention properties, and 1-house adhesion.

As a method to solve these deficiencies and α, for example, there is a method of coating the surface of a soft vinyl chloride resin film with acrylic If resin to prevent dust from adhering to the surface of the soft vinyl chloride resin film. However, not only is the coating agent expensive, but the film manufacturing process and the dustproof film forming process are separate processes, resulting in high film production costs.

Furthermore, even if an acrylic resin film is formed, the antifogging agent contained in the vinyl chloride resin layer will condense on the inner surface and be washed away by falling water droplets when used as an agricultural coating material. After about two years, the antifogging properties deteriorate to the point where they are no longer practical.

In other words, even if the deterioration in dust resistance is kept to a minimum, water droplets from inside the covering material will fall onto the cultivated crops, causing pollination problems and disease outbreaks, so it is necessary to renew the covering material. Is required.

Additionally, in order to improve opening and closing operations during ventilation, the surface of the film is embossed to give it a satin finish, or fillers are mixed into the film to make the film surface uneven, but these measures not only reduce transparency, but also It has the disadvantage of reducing the strength of the film.

On the other hand, PE film has poor heat retaining properties, and in order to improve heat retaining properties, inorganic fillers, various polymer plasticizers, and other additives are added! ! However, there are disadvantages such as increasing the cost of the PE film and deteriorating the physical properties of the PE film.

As described above, all of the current covering materials have some drawbacks, and a satisfactory sleeping film has not yet been obtained.

"Problem to be solved by the invention, α" The present inventors have improved the durability of transparency and handling workability without losing the excellent properties of the conventional agricultural soft vinyl chloride υ[t film. As a result of repeated research, we found that a PE film with good spreadability and dust resistance was applied to the surface of the vinyl chloride <31 fat film of the base layer.
With OW in mind, thin films of PE film are strongly laminated via ethylene-vinyl acetate copolymer, and this multilayer film provides long-lasting transparency, weather resistance, heat retention, flattenability, and anti-fog properties.・Excellent in house adhesion, dustproofing, spreading workability, opening and opening workability during ventilation, and soil hardening, as well as economic efficiency (low production cost), especially in sustainability of transparency and handling. A flexible vinyl chloride resin film for agricultural use with excellent workability has been completed. That is, the object of the present invention is to produce soft vinyl chloride-based Mjllll for agricultural use.
To provide a flexible vinyl chloride resin film for agricultural use that has improved persistence of transparency and handling workability without losing the excellent properties possessed by film.

[Means for Solving the Problems] The essence of the present invention is to laminate a polyethylene film on one side of a soft vinyl chloride resin film via an ethylene-vinyl acetate copolymer, and A flexible vinyl chloride resin film for agricultural use that forms an anti-fog coating on its surface.

The present invention will be explained in more detail below.

In the present invention, the agricultural soft vinyl chloride resin film is formed with a ratio of 3/i, and the surface layer (outer layer of the greenhouse) is a polyethylene film with good stain resistance (dust resistance) and slipperiness (workability). is configured to be

The polyethylene that forms the outer layer of the greenhouse of the agricultural soft vinyl chloride resin film of the present invention has a melt index (
1,5 to 15g/10a+in and density 0.9
Preferably, the ethylene polymer is obtained by radical polymerizing ethylene in the range of 15 to 0.935 g/cts under high pressure. May contain melt index of 0.5g/l 0
If it is less than L6in, it has a high melt viscosity and is difficult to form into an i-film, and if it is more than 15g/10+ain, it is not preferable because it has a low melt viscosity, poor moldability, and a decrease in 811 mechanical strength. If the density is less than 0.915 g/cm', the rigidity will be low and the film will be soft, so it is not preferable. If the density exceeds 0.935 g/cm', the mechanical strength, especially the impact strength, will be lowered, so it is not preferable.

The melt index in the present invention is 1. JIS
This is a value measured with K-6760.

The ethylene-vinyl a-acid copolymer used in the middle layer of the agricultural soft vinyl chloride resin film of the present invention is a copolymer of ethylene and vinyl acetate obtained by radical polymerization under high pressure, Vinyl acetate content concentration is 19 to 41 u+t%, preferably 25 to 41 wt%, melt index is 1 to 60 g/10 ll1in
Preferably.

An ungrooved product with a vinyl acetate concentration of 19 wt% has a weak interlayer adhesive strength with a soft vinyl chloride film, causing a practical problem.41. If it exceeds wt%, the melt viscosity is low and the moldability is poor, so it is not preferable.

Soft vinyl chloride base layer in the present invention! ! Al11 film is a film made of a composition whose main components are vinyl chloride resin, plasticizer, and stabilizer, and where necessary, an i-blocking agent, ultraviolet M absorber, antioxidant, and processing aid are added. The above composition also contains various 85 fat additives such as lubricants, heat stabilizers, antioxidants, stabilizing aids, heat retention improvers, antistatic agents, fungicides, algaecides, and coloring agents. It's okay to stay.

Vinyl chloride (fat composition (hereinafter referred to as rpvcirt composition)
In addition to vinyl chloride homopolymer, vinyl chloride resin, which is a component of
↑Mukitasen combines this unit with Tsuneji V-Nyl (monomers that can be combined with Kitami are vinylidene chloride, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid, itaconic acid, acrylic acid, and acrylic esters) methacrylic acid, methacrylic acid esters, etc.

The vinyl chloride <14 fat may be used alone or in a mixture of two or more. Vinyl chloride resins are conventionally known using suspension polymerization methods, emulsion polymerization methods, emulsion-suspension polymerization methods, solution polymerization methods, bulk polymerization methods, etc. ! By any means! !
! It could be something left behind. The degree of polymerization of the vinyl chloride-based 435 fM is preferably selected from the range of 800 to 2,500.

Examples of plasticizers used in PVC compositions include G-n
- Hepthalic acid plasticizers such as octyl 7-talate, di-2-ethylhexyl 7-talate, dibenzyl 7-talate, diindecyl 7-talate, nododecyl 7-talate, and diindecyl 7-talate; isophthalic acid-based plasticizers such as diisooctyl isophthalate agent; anopic acid plasticizer such as non-n-butyl 7 dibate and dioctyl adipate;
Maleic acid plasticizers such as '-butyl maleate; Citric acid plasticizers such as tri-n-butyl citrate; Itaconic acid plasticizers such as monoitaconate; Oleic acid plasticizers such as butyl oleate; Examples include ricinoleic acid plasticizers such as /Rate. These plasticizers are
One type or a combination of two or more types may be used. The blending amount of these plasticizers is 30 parts per 100 parts of vinyl chloride resin in order to balance the flexibility and strength of the film.
・It is preferable to select from a range of 770 parts by weight.

Also, trioctyl phosphate, triphenyl phosphate 7
Phosphate ester plasticizers such as triphenyl phosphate, trixylenyl phosphate, diphenyl octyl phosphate, nophenyl crepe phosphate, triethylphenyl phosphate, etc. are 1 to 710 parts by weight per 100 parts by weight of vinyl chloride resin. It is desirable that

Epoxy compounds used in PVCML bonnet include epoxidized soybean oil, evoquinated linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized fish oil, epoxidized polybutadiene, methyl epoxy stearate, butyl epoxy stearate, Epoxy/2-ethylhexyl stearate, epoxy stearyl stearate, tris(epoxyprobyl) in cyanurate, epoxidized castor oil, epoxidized soybean oil, epoxidized linseed oil fatty acid ester, 3-(2-xy7xyl) )-1,2-epoxypropane, bisphenol-A・
Examples include diglycinol ether, vinylcyclohexene dieboxide, and a polycondensate of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin.

The blending amount of these epoxy compounds is 1 part vinyl chloride resin.
00 parts by weight (ana') 0.7% 7 parts by weight is desirable.

Examples of compounds that can be used as ultraviolet absorbers in the PvC composition include the following.

Benzotriazole UV absorber-1-2-(2'-
Hydroxy-3',5'-not-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole , 2-(2'-
Hydroxy-3'-tert-7mil-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(
2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5'-chlorobenzotriazole, 2-(2
°-Hydroxy-3'-isoptyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'
-hydroxy-3',5'-notcrt-butylphenyl)benzotriazole, 2-(2'-hydroxy-
5'-methylphenyl)benzotriazole, 2-(2
'-tDroxy-5' (1,1,3,3-tetramethylbutyl)phenyl)benzotriazole.

Benzo-7ene-based ultraviolet absorber ---2,2°-nobidroxy-4-methoxybenzophenone, 2゜2゛-dihydroxy-4,4゛-dimethoxybenzo-7ene, 2.
2'4.4'-tetrahydroxyben V7ene, 2-
Hydroxy-4-methoxybenzo-7enone, 2,4-dihydroxybenzo-7enone, 2-hydroxy-4-dihydroxybenzo-7enone.

Salicylsan-based ultraviolet absorbers - 1-7enyl salicylate, rose octylphenyl salicylate.

The ultraviolet absorbers can be used alone or in combination of two or more. Among those exemplified above, benzotriazole-based ultraviolet absorbers and benzo-7/-based ultraviolet absorbers are particularly preferred, and the blending amount is 0.1 to 3 parts by weight per 100 parts by weight of vinyl chloride resin. is desirable.

As a light stabilizer, 4-7 setoxy 2,2.6°6-
Chitramethylpiveridine, 4-stearoyloxy-2
, 2,6,6-titramethylbiveridine, 4-acryloyl oxine-2,2,6,6-titramethylbiperinone, 4-(phenylacetoxy)-2,2,6,6-titramethyl Piveridine, 4-(phenoxyacetoxy)
-2,2,6,6-titramethylbiverinone, 4-cyclohexanoyloxy-2,2,6,6-titramethylpiveridine, 4-benzoyloxy-2.2,6.6-
Titramethylbiveridine, 4-(o-chlorobenzyloxy)-2,2,6,6-titramethylbiveridine,
4-(I-monochlorobenzoyloxy)-2,2,6,6-titramethylpiveridine, 4-(p-chlorobenzyloxy)-2,2,6,6-titramethylbiveridine, 4-(
o-)ruyloxy)-2,2,6,6-titramethylbiverinone, 4-ynenicotinoyloxy-2,2,6
, 6-titramethylbiperidine, 4-(2-70yloxy)-2,2,6,6-titramethylbiperidine, 4
-(β-7toyloxy)-2゜2.6.6-titramethylbiperinone, bis(2,2゜6.6-tetramethyl-4-piperidyl)oxalate, bis(2,2,6
, 6-tetramethyl-4-piperinor)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)
Adipate, bis(2゜2.6.6-tetramethyl-4
-piperinol)sepacate, bis(2,2,6,6-tetramethyl-4-biveridyl)7malate, bis(2,
2,6,6-tetramethyl-4-piperidyl)hexahydro7talate, bis(2,2,6,6-tetramethyl-4-piperinor)terephthalate, tris(2,2
6゜6-tetramethyl-4-piperinor)benzene, 1
．． 3.5-) recarboxylate, tris(2,2゜6
．． 6-tetramethyl-4-piperidyl)triazine-2
, 4,6-tricarboxylate, tris(2,2,6
, 6-tetramethyl-4-piperidyl) nitrilotriacetate, tris(2,2,6,6-tetramethyl-4
-piperidyl)butane-1,2,3-tricarboxylate, tetrakis(2,2,6,6-tetramethyl-4
-piperidyl)propane-1゜1.2.3--tetracarboxylate, tetrakis(2,2,G,6-tetramethyl-4-piperinor)butane-1,2,3,4-tetracarboxylate, tetrakis (2, 2, 6, 6-
Tetramethyl-4-piperidyl)propane-1,1,3
, 3-tetracarboxylate, tetrakis(2,2,
6,6-tetramethyl-4-piperidyl)etheno-1,
1,2,2-tetracarboxylate, tris(2,2
, 6,6-tetramethyl-4-piperidyl)-2-7cetoxypropane-1.2.3-)licarboxylate,
Examples include tris(2,2,6,6-tetramethyl-4-piperidyl)-2-hydroxypropane-1,2,3-tricarboxylate. The blending amount of these light stabilizers is preferably 0.05 to 3 parts by weight per 100 parts by weight of the vinyl chloride resin.

Examples of lubricants and heat stabilizers that can be used include polyethylene wax, liquid paraffin, stearic acid, zinc stearate, fatty alcohols, calcium stearate, barium stearate, barium ricylate, butyl tin laurate, and Butyltin malate, 7
Examples include ethers, β-diketone compounds, and the like.

These lubricants and heat stabilizers can be used alone or in combination of two or more.

Compounds that can be used as antioxidants include 2.6-
Not-tert-butyl-4-methylphenol, 2,2
゛-Methylenebis(6Lert-butyl-4-ethyl7
E7-rupionate and the like can be mentioned. These antioxidants can be used singly or in combination of two or more.

Examples of compounds that can be used as antistatic agents include polyoxyethylene alkylamine, polyglycol,
Ether, sodium p-styrene sulfonate, etc. can be mentioned. These antistatic agents can be used alone or in combination of two or more.

Compounds that can be used as stabilizing aids include triphenyl phosphite, nooctylphenyl phosphite,
Examples include tris(7-nylphenyl) phosphite, nophenylisodecyl phosphite, trilauryl trithiophosphite, diphenyl acinato phosphite, and dioctyl acid phosphite. These stabilizing aids can be used alone or in combination of two or more.

Compounds that can be used as fungicides and algaecides include 2.
+4t5+6-titrachloroiso7lyronitrile, 1
0,1 0°-oxybis727xialsine, 2-(
4-thiazolyl)-benzimiguzole, N(fluorodichloro/tilthio)7talimide, N-tumethyl-N
'-Phenyl-(N'-70 lonochloromethylthio)sulfamide, paraoxybenzoic acid ester, 5-promo 5-nitro-1,3-dioxane, 2.3.5.6-
Examples include tetrachloro-4-methylsulfonylbilinone, 3-methyl-4-chlorophenol, N(tetrachloroethylthio)7talimide, tributyltin laurate, and the like. These compounds can be used alone or in combination.

Examples of colorants that can be used include 7-thalocyanine blue, 7-thalocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc white, permanent red, quinacridone, and carbon black. These colorants can also be used alone or in combination of two or more.

It is desirable to use the following various resin additives within a range that does not deteriorate the properties of the composition, usually within a range of 5 parts by weight or less per 100 parts by weight of the vinyl chloride resin.

To obtain a vinyl chloride resin composition, for example, a 7-talic acid group plasticizer, a phosphate ester plasticizer, an epoxy compound, an ultraviolet absorber, and a bamboo piperinone-based compound are added to a vinyl chloride-based resin. The mixing method for each resin additive is required.
The resin composition obtained in this way can be weighed and used as a soft vinyl chloride resin layer of the present invention by using a ribbon blender, super mixer, or other mixing machine known from Jubei. What about the above? The JF fat composition is used as a tri-blend which is cooled and dried to avoid lumps, or it is kneaded with a known kneader such as a Banbury mixer or a Connie Goo mill, and then crushed or shredded to form a granular solid ( You can use either method (as a pellet tip) or use either method.

The agricultural soft vinyl chloride resin film of the present invention can be manufactured according to a conventional method. For example, by in-7 resin molding or T-guy molding, the above-mentioned resin compositions or (kt resin compositions) are fed into one die from separate extruders and laminated and integrated inside or outside the die, so-called co-extrusion. The laminating method involves forming resin films in advance, applying adhesive (titanate, polyethyleneimine or incyanate resin, etc. are usually used) to these resin films, and passing the film through a drying oven to evaporate the solvent. A method of producing an 81j layer by overlapping the film to be laminated on top of the dried film and press-bonding it under heat;
Polyolefin resin is extruded into a film using the T-Guy method, and while the film is still in a molten state, it is allowed to flow onto another resin film coated with an adhesive if necessary, and immediately passed between rolls for lamination. For example, how to do this.

In the latter two manufacturing methods, two or more types of films or sheets are first formed by calendering, extrusion, etc., and then laminated into wood, which simplifies the process and reduces production costs. In addition to being expensive, laminating methods that use adhesives have problems such as contaminating the working environment because the solvent in the adhesive evaporates into the atmosphere.

Furthermore, in the case of films or sheets with high elongation, it is difficult to uniformly apply the adhesive, which tends to cause bubbles and wrinkles, and also tends to cause defects such as weak adhesion between each layer, so coextrusion is not recommended. It is most preferable to mold them in one piece.

Among them, the method of co-extruding a flat sheet or cylindrical object using a composite T die or a composite cylindrical die, taking it out in the usual way, and then heat-treating it if necessary improves interlayer adhesion and productivity. This is the most desirable method for

The agricultural soft vinyl chloride resin film according to the present invention is
- A film based on an anti-fog paint is formed on the surface, and this film based on an anti-fog paint is used as the inner surface when the film is used in a house etc. to prevent water droplets from adhering to it. It fulfills the function of

Anti-fog paints include the following:

1) 15w of hydrophilic acrylic compound as an active ingredient
Contains acrylic polymer containing t% or more.

2) Those containing alumina sol as an active ingredient.

3) Those containing coroiglucilipotency as an active ingredient.

4) A block copolymer containing a hydrophobic molecular chain block and a hydrophilic molecular chain block in the molecule as an active ingredient.

The acrylic polymer in 1) above refers to an acrylic polymer containing a hydrophilic acrylic compound in an amount of 15 wL% or more, particularly preferably 5°wt% or more. Hydrophilic acrylic compounds include hydroxyalkyl (meth)acrylates.

1) Hydroxyalkyl (meth)acrylates used in the production of acrylic polymers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (
meth)acrylate, 2-hydroxypropyl(meth)
Acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate,
Examples include 4-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and the like. This is C
) may be a homopolymer of 11, or a copolymer containing these hydroxyalkyl(meth)acrylate)H as a main component and other monomers copolymerizable with them.

- The alumina sol constituting the active ingredient in 2) above has an average particle size of 200 μm or less and 17 μm or less.

This alumina sol is combined with water and surfactant,
It is preferable to use it in a solid content of 0.05 to 10 wt% (for the entire antifogging coating).

The alumina sol may be a commercially available product itself, or an aqueous sol obtained by dispersing commonly available alumina powder in water. When alumina sol is dispersed in water at a high concentration, it exhibits so-called thixotropy, meaning that the viscosity of the dispersion increases rapidly, making it difficult to obtain a homogeneous dispersion. However, a medium shear internal stirrer such as a colloid mill is used. A homogeneous dispersion can be obtained. Furthermore, by mixing coroiglusilic acid into this dispersion, the viscosity of the dispersion can be lowered.

- L 2 Is the surfactant used in combination with the paint containing alumina sol as an active ingredient non-ionic 1? SWL surfactants are preferred, and specific examples include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, fatty acid alkylolamides, and cellulose ethers. can give. The proportion of these surfactants in the antifogging paint is preferably 0.05 to 15 wt%.

Similar to the alumina sol described in 2) above, the colloidal silica constituting the active ingredient in 3) above has an average particle diameter of 200 millimicrons or less. Alumina sol can be combined with water and surfactant to produce a solid content of 0.05'vlOu+
It is preferable to use it as t% (based on the entire anti-fog coating).

In most cases, the particle surface is negatively charged, so it is not preferable to use a particle that is negatively charged. This is because the particle surface of the alumina sol mentioned above is positively charged, so when the negatively charged colloidal silica and the positively charged alumina sol are mixed, the mixed dispersion rapidly changes. They aggregate, gel, and cause poor dispersion. Therefore, it is preferable that the particle surface of the colloidal silica be positively charged.

Similar to the alumina sol in 2) above, the surfactant used in combination with the paint containing colloidal silica as an active ingredient in 3) above,
Nonionic surfactants are preferred, and specific examples include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters,
Examples include fatty acid alkylolamides and cellulose ethers. The proportion of these surfactants in the antifogging paint is preferably 0.05 to 15 wt%.

The alumina sol and coroiglu silica in 2) and 3) above are
Each j) may be used alone or both may be used in combination. When combining the two, the weight ratio of Flögl Siri force and alumina sol is 80 to 20.
The ratio is preferably from /20 to 80 (the whole being 100).

- The block copolymer in 4) above refers to a copolymer containing a hydrophobic molecule block and a hydrophilic molecule block in the molecule.

The hydrophobic molecular blocks of the pro-7 copolymer in 4) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hequinyl acrylate, heptyl acrylate, and octyl acrylate. , methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, hebutyl methacrylate, octyl methacrylate, acrylonitrile,
(Meth)acrylate ζ 1 body such as methacrylate trile; Vinyl aromatic 1'F prototype body such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene; Tzene monomer such as butadiene, isoprene, chlorobrene; Vinyl acetate , a type of homopolymer of a jlj-mer such as a vinyl monomer such as vinyl stearate, or a copolymer of two or more types of monomers.

Hydrophilic molecular chain blocks of the block copolymer in 4) above include hydroxymethyl (meth)acrylate, 2-
Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate acrylate, hydroxyalkyl (meth)acrylates such as 6-hydroxyhexyl (meth)acrylate; methacrylic acid, acrylamide, methacrylamide, diacetone acrylamide, noacetone methacrylamide,
A homopolymer of one type of acrylic monomer ring such as methylol acrylamide and methylol methacrylamide, a copolymer of two or more monomers, or a copolymer of one or more of the monomers listed above and these monomers. Copolymers with other monomers.

Other copolymerizable monomers include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, itaconic acid, itaconic acid ester, and the like.

- In order to produce a block copolymer containing a hydrophobic polymer chain prong and a hydrophilic molecular chain block in the molecule, it is possible to use a known addition polymerization method, condensation polymerization method, etc. . In terms of construction, JP-A-53-149918
Publication, [Reinforced plastic included] No. 298:) fp
It is preferable to use a method using polymeric peroxide, as described in pages J107 to J112.

The block copolymer using polymeric peroxide (polyPO) is as shown in the following 70-sheet! l! It is possible to send

Monomer (1) Block copolymer 'It ffi form I and monomer (2) are selected from compounds that form a hydrophilic molecular chain block, and the other from compounds that form a hydrophobic molecular chain block.

The block copolymer has a hydrophobic molecular block and a hydrophilic molecular chain block in a weight ratio of 10 to 90/90 to 10 (
(total number is 100).

If the proportion of the hydrophilic molecular chain block is too much higher than the above range, the adhesion between the film surface and the coating formed by the block copolymer will decrease, and the sustainability of the hydrophilicity of the film surface will be poor, which is undesirable. .

On the other hand, if the proportion of the hydrophilic molecule block is less than the above range, the adhesion to the film surface will improve, but the hydrophilicity of the coating will decrease, which is not preferable.

A particularly preferable weight ratio of the hydrophobic molecule block and the hydrophilic block is 20 to 50/80 to 50 (the whole is 1
00).

The block copolymer can be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

In the present invention, a coating of the block copolymer is formed on the remaining surface of the flexible vinyl chloride-based VM film. In order to form a film, it is preferable to dissolve or disperse the block copolymer in a solvent, apply this solution or dispersion to the surface of the film, and evaporate the solvent.

According to experiments conducted by the present inventors, the preferred solvent for dissolving or dispersing the block copolymer is a good solvent for both hydrophobic molecular chain blocks and hydrophilic molecular chain blocks, and a good solvent for hydrophobic molecular chain blocks and hydrophilic molecular chain blocks. It is better to use a solvent mixed with a poor solvent for the chain block.

Examples of good solvents for both components include methyl cellosolve, ethyl cellosolve, noacetone alcohol, acetic acid esters, and ketones.

Examples of the poor solvent for the hydrophobic molecular chain block include lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol, either singly or in a mixture of two or more.

- The mixing ratio of the above two types of solvents can be selected depending on the composition of the block copolymer and the viscosity of the block copolymer solution. The viscosity of the block copolymer solution is preferably such that it can be easily applied to the film surface.

The solution in which the above block copolymer is dissolved or dispersed includes:
An appropriate amount of surfactant can be blended for the purpose of improving the applicability (viscosity) of the solution glue (on the surface of the fat molded product) or for the purpose of supplementing hydrophilicity. Preferred surfactants are It is an ionic surfactant.

The amount of these surfactants added to the solvent is preferably 20 parts by weight or less per 100 parts by weight of the block copolymer. This is because if the amount exceeds 20 parts by weight, the durability of the hydrophilic property of the coating may decrease.

The three types of anti-fog paints explained above are used as a base material of soft vinyl chloride 84M! The remaining sides of the film can be coated by coating methods known per se.

In order to volatilize the solvent or aqueous medium after coating, the coated surface may be dried. Drying methods include forced drying such as hot air drying, infrared RF drying, far infrared drying, and natural drying by leaving at room temperature. Conditions for forced drying are preferably selected at a temperature range of 50 to 150° C. for 30 seconds to 5 minutes.

vf, the higher the drying temperature, the shorter the drying time can be.

Note that, before applying the antifogging dye, the surface of the film may be pretreated as in the case of applying the dustproof paint.

In the present invention, the coating formed on the remaining surface of the base film (the surface on which the polyethylene resin film is not applied) based on the antifogging paint includes the coating when an Angoo coating is applied. The amount after dry assimilation is preferably in the range of 0.1 to 58/112.

When it is less than 0,1 g/+a2, the durability of anti-fog properties is poor, and it is more than 5H/+o2〉Rebellion 1+7 Norse/
7'I Hakata-v1 heavy chain-M (jinshita red 1 not included. Among the above ranges, a range of 0.2 to 3 g/n2 is particularly preferred.

[Effects of the Invention] When the laminated film obtained by the present invention is used as a covering film for a greenhouse, house, tunnel, etc.,
Conventional agricultural single film (soft vinyl chloride film,
By incorporating the strengths of each individual film and laminating them together, the film has the characteristics of a soft vinyl chloride resin film, something that could never be achieved with polyethylene film or ethylene-vinyl acetate copolymer film. It has good antifogging properties and long-lasting transparency, is less sticky, and has excellent handling and workability, so it has extremely high practicality as an agricultural film that can be used for a long period of time.

"Examples" Next, the present invention will be described in detail based on Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1, Comparative Example 1 Beret A: PVCjlt product g IJ hinyl chloride (I' = 1300) 100 (
fftjrlffls) stabilizer (barium-zinc composite stabilizer 'I 1, 5 (, / ) (barium stearate) 0.5 (//) (zinc stearate)
0, 5 (//) Bisamide
Q, 5 (//) UV 4Q absorption variable light stabilizer
After mixing the above compositions in a Henschel mixer and cooling,
The mixture was kneaded using goo and extruded at a temperature of 170°C to form a pellet.

Berent B: Ethylene-vinyl acetate copolymer (EVAH
Commercial product> Vinyl acetate content concentration 28 wt%, melt indica.

Bellet C: Polyethylene (commercial product) A pellet of polyethylene with a density of 0.918 F1/cm and a full index of 12 H/10 min was used.

Anti-fog resin can be made using the method below! T! Lv, Formative application and scraping [) ft I had vomiting.

Methyl methacrylate GO (polydisperse) Butyl methacrylate 30 (//) Trimethylaminoethyl methacrylate Chlorine 10 (,/) Benzoyl peroxide 0.5 (0) Isopropyl alcohol 300 (// ) Charge the above composition into a flask and add N2 $ The reaction was carried out at a temperature of 80° C. for 7 hours under an ambient atmosphere. Isopropyl alcohol is added to the obtained reaction product by IR.
In addition, the paint had a solid content of 13% by weight.

Anti-fog 1 (oil layer coating agent E) was prepared by the following method.

Colloidal silica Catalyst Kasei Co., Ltd. Cataloid SE-30 0.5 (heavy, ff1ffl Q, 5 (n)) Aqueous methoxycellulose 0.1 (it) Shin-Etsu Chemical Co., Ltd. Metrose 653 H50 Peek-in ion water 1oo(n) The above composition was dispersed and mixed using a homogenizer.

Use a 65φ extruder for pellet A, and use a 40mm extruder for pellet B.
Using a φ extrusion rock, Beret) C was extruded at 180'C using a 40φ extrusion rock, and fed to a 3-layer co-extrusion composite T gui to form a molten film consisting of 3 scraps. The film was cooled by guiding it onto a casting roll at 50°C placed close to the goose, and forming a PVC film layer of 110μ, an EVA film layer of 20μ, and a PE film layer of 1.
A laminated film of 1000 IlIl was obtained, consisting of 4μ.

Next, on one side of the WI film (the side on which the polyethylene street resin film is not laminated), a coating agent for forming a magnetic film is applied by roll coating according to the method described in 1if, so that the thickness after drying is 1μ. was applied and dried with hot air. Furthermore, a hydrophilicity-imparting coating agent made of Frogl Silica prepared by the above-mentioned method was applied to the surface by a roll coating method in the same manner as the acrylic resin, and then dried with hot air.

In addition, as a comparative example, commercially available vinyl chloride resin 7 (/
1,4 (S-PVC, wall thickness 100 u) and tl) 14
A single-layer film of polyethylene film for X (S poly, Nikki gioooμ) was used.

The following properties of the laminated film and single layer film were investigated.

Dustproof properties> The test film was coated on a pipe house (opening 3 m, depth 51, ridge height 1.5, roof slope 30 degrees) installed in a test field in Shigun, Mie Prefecture, with the polyethylene surface on the outside of the house. , 2 from February 1980 to February 1986
An annual expansion test was conducted.

Wave VC555 mm after collecting the film after the stretching test;
PS-2U model).

The measurement results were displayed as follows.

◎... Light transmittance is 80% or more ○... Light transmittance is in the range of 65-79% Δ... Light transmittance is in the range of 45-64% ×... Light rays Workability when transmittance is less than 45%> Judgment was made based on ease of handling when spreading the laminated film into a tunnel or house.

0... Not sticky, easy to work with Δ... Slightly sticky, making it difficult to work ×... Strongly sticky, difficult to work with, heat retention> 5-25 microns ( Judgment was made based on the transmittance of infrared rays with a wavelength of μ).

○...30% or less Δ...30-70% ×...70% or more anti-fogging property> The test film was placed in a single-roofed house facing south in a test field in Shigun, Mie Prefecture. Expanded in June 1958, 60
After 24 months (up to June 2016), the condition of water droplets adhering to the house side surface of the film was observed with the naked eye. The observation results were displayed as follows.

◎...Water droplets attached to the film surface (the side facing the inside of the house) coalesce and spread into a thin film, and the area of this thin film portion covers more than 1/2 of the film surface (same as above).

○: Water droplets attached to the film surface (same as above) are observed to coalesce and spread into a thin film, but the area of this thin film portion is less than 1/2 of the film surface (same as above).

Δ: Coalescence of water droplets adhering to the film surface (same as above) is observed, but formation of a thin film-like portion is not observed.

×: Coalescence of water droplets attached to the film surface (same as above) is not observed.

House Wj Adhesion> Judgment was made based on the tension of the m1Vj film when it was stretched on the frame of a house or tunnel.

○: There are no gaps between the frame and the film, and there are no walnuts or wrinkles overall.

Δ: There is a slight gap between the frame and the film, and there are walnuts and wrinkles here and there.

×: There is a gap between the frame and the film, the tension is poor overall, and there are many walnuts and wrinkles.

Weather resistance> The test film was exposed to sunlight for two years from June 1980 to June 1988 on a stand facing south and tilted at 45 degrees to the ground outdoors in Shigun, Mie Prefecture. The change in appearance of each film was observed and evaluated with the naked eye. The evaluation results of "weather resistance" each have the following significance.

○...No change.

○×: Slight brown spots are observed.

Δ... Brown spots are observed.

ΔX...Many brown spots are seen.

X: Browning occurs over the entire surface.

<Transparency> The transparency of the obtained laminated film was visually determined.

O...Transparent Δ...Slightly cloudy Bleed and eruption were determined visually.

○...The surface is transparent like the laminated film at the time of manufacture,
Condition in which viscous oily substance is not observed Δ... Condition in which viscous oily substance is slightly spouted ×... Condition in which viscous oily substance is spouted from surface to surface The results are shown in Table 1. .

Example 2 N008 Benz) A and Beret C used in Example 1
was extruded at 180°C using a 40φ extruder, EVA pellets with different concentrations of vinyl acetate were extruded at 180°C using a 20φ extrusion rock, and fed to a composite T-guid for two-layer coextrusion to separate each resin layer. The sheet was made up of two layers with a thickness of 300μ.

The interlayer adhesive strength between each resin of the thus obtained laminated sheet was measured by T-peel.

The results are shown in Table 2.

Claims (5)

[Claims] (1) Agricultural soft vinyl chloride resin film with a polyethylene resin film laminated on one side of the soft vinyl chloride resin film via an ethylene-vinyl acetate copolymer, and an anti-fog coating formed on the other side. . (2) The soft vinyl chloride resin of the base layer contains 1 to 1 phosphate ester plasticizer per 100 parts by weight of the vinyl chloride resin.
0 parts by weight, 0.7 to 7 parts by weight of epoxy compound, 0.1 to 3 parts by weight of ultraviolet absorber, and/or 0.0 parts by weight of light stabilizer.
The agricultural soft vinyl chloride resin film according to claim 1, which contains 5 to 3 parts by weight. (3) The agricultural soft vinyl chloride resin film according to claim 2, wherein the light stabilizer is a hindered amine compound. (4) The agricultural soft vinyl chloride resin film according to claim 1, wherein the vinyl acetate content concentration of the ethylene-vinyl acetate copolymer is 19 to 41 wt%. (5) A patent in which the active ingredient of the anti-fog coating is 1) a hydrophilic acrylic polymer, 2) an alumina sol, 3) colloidal silica, and 4) a block copolymer containing a hydrophobic molecular chain and a hydrophilic molecular chain in one molecule. The agricultural soft vinyl chloride resin film according to claim 1.