JP3129201B2 - Agricultural vinyl chloride resin film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin film for agricultural use. More specifically, the present invention relates to a vinyl chloride-based resin film for agricultural use having excellent durability, in which vinyl chloride-based resin fibers are composited.

[0002]

2. Description of the Related Art In recent years, in order to efficiently cultivate useful plants, promotion cultivation in a house or a tunnel has been actively performed. As a material for covering the house or the tunnel, a vinyl chloride resin film is frequently used because of its excellent weather resistance, transparency, heat retention and the like.
However, the vinyl chloride resin film is strong wind or
At low temperatures, the film becomes hard and easily breaks. In order to prevent the breakage, to randomly intersect polyester resin thread or strip-shaped tape to make a grid-like material,
Laminate in a lattice shape and laminate it with a polyvinyl chloride film to form a film (Japanese Patent Publication No. 40-2519)
1, JP-A-2-100621, JP-A-6-62682)
Has been proposed. However, they did not have sufficient durability.

Further, a reinforced vinyl chloride resin laminated film for agricultural use in which a reinforcing thread composed of multifilaments of a vinyl chloride or vinylidene chloride resin bundled with a binder of a resin emulsion is inserted (Japanese Patent Laid-Open No. 8-16908)
9) has been proposed. However, although these films are effective in preventing tearing, long-term outdoor exposure as a coating material causes a change in the appearance of the film,
There was a problem in long-term use.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a vinyl chloride resin film for agricultural use which is excellent in durability without deterioration in physical properties or change in appearance even when used for a long period of time.

[0005]

Means for Solving the Problems The present inventors have solved the above-mentioned problems by subjecting vinyl chloride resin fibers to a surface treatment comprising a specific substance. Thus, the gist of the present invention is to provide a vinyl chloride resin for agricultural use in which a yarn group composed of a vinyl chloride resin fiber surface-treated with silicone oil is sandwiched between two vinyl chloride resin films. Exists in resin film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the vinyl chloride resin is vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith by a conventional method such as a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method or an emulsion polymerization method. It is meant to include all products manufactured. Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate; and dibutyl. Maleates such as maleate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; cyanides such as acrylonitrile and methacrylonitrile Α-olefins such as vinyl chloride, ethylene, propylene and styrene, vinylidene chloride and vinyl halide other than vinyl chloride such as vinylidene chloride and vinyl bromide Diallyl phthalate, polyfunctional monomers such as ethylene glycol dimethacrylate and the like, of course, the comonomer is not limited to those described above. The polymerization degree of the vinyl chloride resin can be selected in the range of 700 to 2500, and is preferably 700 to 1800.

In order to produce vinyl chloride resin fibers, these resins may be produced by a method such as dry spinning, melt spinning and wet spinning. As the vinyl chloride resin fiber used in the present invention, a monofilament and / or a multifilament can be used. The thickness of the fiber is preferably in the range of 300 to 3000 denier, especially 600.
~ 3000 denier is preferred. The thickness of one multifilament is in the range of 1 to 300 denier,
A range of 250 denier is preferred. The overall thread thickness is 3
If the denier is less than 00 denier, the fiber strength is insufficient and the propagation of tears cannot be prevented. On the other hand, if it exceeds 3000 denier, the fiber strength increases but the transmittance is undesirably reduced.

The density of the fiber is preferably 3 to 30 g / m 2, more preferably 5 to 25 g / m 2. If it is less than 3 g / m 2, the occurrence of tearing cannot be prevented, while if it exceeds 30 g / m 2, the light transmittance is undesirably reduced. In the present invention, the vinyl chloride resin fiber refers to a fiber or a yarn made of the fiber. The surface treatment may be performed at the fiber stage or as a yarn.

[0009] Silicone oil for surface treatment is a fluid oil having a relatively low degree of polymerization and mainly composed of a linear or branched diorganopolysiloxane.
Specifically, for example, dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, amino-modified silicone oil, alkyl-modified silicone oil, phenyl-modified silicone oil, carboxyl-modified silicone oil, higher fatty acid-modified silicone oil, epoxy-modified silicone oil,
Vinyl group-containing silicone oil, alcohol-modified silicone oil, polyether-modified silicone oil, alkyl / polyether-modified silicone oil, fluorine-modified silicone oil, polyoxyalkylene-modified silicone oil, alkoxysilane, reactive siloxane oligomer, and their structures And other silicone elastomers. These may be used alone or in combination of two or more.

For surface treatment of vinyl chloride resin fibers, silicone oil may be used as it is, or may be dissolved or emulsified in a solvent. Solvents for dissolution include alcohols, for example, hexadecyl alcohol, octadecyl alcohol and the like: esters, for example, dioctyl sebacate, dilauryl phthalate, isooctyl stearate, isooctyl stearate, isopropyl myristate and the like.

In the case of emulsification, a known emulsifier may be used. For example, a nonionic surfactant such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether, a cationic surfactant such as an alkyl ammonium salt and an alkyl benzyl ammonium salt, and an anionic surfactant can be used. The amount of the emulsifier used is 0.1 to silicone oil.
1% to 20% is preferred. If it is less than 0.1%, no emulsified product is formed, and if it is more than 20%, durability is adversely affected, which is not preferable.

The treating agent comprising the silicone oil of the present invention is prepared by dispersing and mixing solid fine particles.
The effect of preventing fusion between the film and the yarn can be increased. As solid fine particles, for example, silica, alumina, water-insoluble lithium silicate, calcium carbonate, talc,
Fine particles such as iron hydroxide, tin hydroxide, titanium oxide and barium sulfate are used, and among them, silica, calcium carbonate, alumina and talc are preferred. These may be used alone or in combination.

The average particle diameter of the solid fine particles used is 15 μm or less, preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm. When the average particle diameter exceeds 15 μm, the yarn tends to be white and devitrified, and when the average particle diameter is less than 0.01 μm, the stability of the treating agent may be lacking, which is not preferable. In addition, it is important that the amount is less than 5% based on the silicone oil.

When used as an emulsion, it is preferable to further incorporate a crosslinking agent. As a crosslinking agent,
Phenol resins, amino resins, amine compounds, aziridine compounds, azo compounds, isocyanate compounds, epoxy compounds, silane compounds and the like, and particularly, amine compounds, aziridine compounds, epoxy compounds It is suitable.

Examples of the amine compounds include aliphatic polyamines such as diethylenetriamine, triethylenepentamine, and hexamethylenediamine; 3,3'-dimethyl-4,
Alicyclic amines such as 4'-diaminodicyclohexylmethane and isophoronediamine; and aromatic amines such as 4,4'-diaminodiphenylmethane and m-phenylenediamine are used. Aziridine compounds include tris-
2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane-tri-β-aziridinylpropionate, tris [1- (2-methyl) aziridinyl] phosphine oxide, hexa [1- (2-
Methyl) -diaridinyl] triphosphatriazine and the like.

Epoxy compounds include epoxidized novolak resins formed by the reaction of epichlorohydrin with the reaction product of bisphenol A or bisphenol F with epichlorohydrin, the resin reaction product of phenol (or substituted phenol) with formaldehyde, epichlorohydrin And aliphatic polyhydric alcohols such as glycerol, 1,4-butanediol, poly (oxypropylene) glycol or similar polyhydric alcohol components, resinous reaction products, and resins obtained by epoxidation using peracetic acid, etc. Is used. In the case of epoxy compounds, it is preferable to use a tertiary amine or a quaternary ammonium salt in combination as a catalyst.

These crosslinking agents can be used in amounts ranging from 0.1 to 30% by weight based on the silicone oil. In particular, the range of 0.5 to 10% by weight is preferable. Further, if necessary, a liquid dispersion medium is further blended. Such liquid dispersion media include hydrophilic or water-miscible solvents including water, and water; monohydric alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, and glycerin. Cyclic alcohols such as benzyl alcohol; cellosolve acetates; ketones and the like.

Further, additives such as an anti-adhesion agent and an antistatic agent can be mixed with the surface treatment agent composed of silicone oil, if necessary. As the anti-stick agent, a metal soap may be used, and examples thereof include aluminum stearate, zinc stearate, and magnesium stearate, and magnesium stearate is particularly preferable.
The amount of these additives is 5% based on the weight of the silicone oil.
The following is preferred.

The surface treatment of the vinyl chloride resin fiber with the silicone oil may be performed by any known coating method such as a roll coating method, a gravure coating method, a reverse coating method, and a dip coating method.

As a drying method for drying the applied silicone oil emulsion, for example, a forced drying method such as a natural drying method, a hot air drying method, or an infrared drying method can be employed. The heating temperature at the time of forcible drying is determined by the resin to be applied, but is 50 to 250 ° C., preferably 70 to 200 ° C.
It is in the range of ° C. The amount of the surface treatment agent attached to the vinyl chloride resin fiber is 0.5 to 0.5 wt.
A range of 30%, especially 2-20% is preferred. If the amount of adhesion to the vinyl chloride resin fiber is less than 0.5%, the durability will not be sufficiently excellent, while if it is more than 30%, the fiber will be too rigid and the fiber will be pinched. It is not preferable because the initial physical properties of the film are reduced.

The composition of the vinyl chloride resin film according to the present invention may contain a plasticizer, an antifogging agent, an antifog agent, a lubricant, a heat stabilizer, an ultraviolet absorber, an inorganic And various additives such as an antioxidant, a stabilizing aid, an antistatic agent, an antifungal agent, an antialgal agent, and a coloring agent.

As the plasticizer, those commonly used for plasticizing vinyl chloride resins are used. For example, low molecular weight polyhydric alcohols having a molecular weight of 250 or less, phthalic acid derivatives, isophthalic acid derivatives, adipic acid derivatives, maleic acid derivatives, citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives and the like can be mentioned. These plasticizers may be used alone or in combination of two or more. The amount of these plasticizers is set to be equal to 100 parts of the vinyl chloride resin in order to balance the flexibility and strength of the film.
It should be selected from the range of 30 to 60 parts by weight with respect to parts by weight.

Other examples include an epoxy plasticizer and an organic phosphate. As an epoxy plasticizer,
There are epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil and epoxy resins. These epoxy plasticizers are added in an amount of 0.1 to 100 parts by weight of the resin.
The amount is from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight. The compounding amount of the organic phosphate plasticizer is
An appropriate amount is in the range of 1 to 10 parts by weight, particularly 2 to 8 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

As the anti-fogging agent, nonionic surfactants are preferable, and ether-type ones such as polyoxyethylene ether, polyoxyethylene alkylaryl ether and polyoxyethylene polyoxypropylene ether, and polyhydric alcohols And ester type such as polyoxyethylene ether of glycerin ester and polyoxyl ethylene ether of sorbitan ester. Hereinafter, suitable nonionic surfactants will be exemplified.

(A) Partial ester of a polyhydric alcohol such as sorbitan, sorbitol, mannitol, mannitol, glycerin, diglycerin and a fatty acid having 12 to 22 carbon atoms. (B) The alkylene oxide is ethylene oxide or propylene oxide. The addition mole number is 1 to 20 mol, and the polyhydric alcohol is sorbitan, sorbitol, mannitol, mannitol, glycerin, diglycerin,
Fatty acid esters of polyoxyalkylene polyhydric alcohols in which the fatty acid has 12 to 22 carbon atoms (c) A mixture of (a) and (b). These mixtures are obtained as mixtures of monoesters, diesters and triesters of polyhydric alcohols. Generally, an ester mixture having a high content of the diester component is preferred.

The amount of the nonionic surfactant is selected from the range of 0.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. In particular, 1.0 to 3.0 parts by weight is appropriate.

Examples of the antifog include fluorine-based surfactants. Specifically, the C of the hydrophobic group of a normal surfactant
Is a surfactant in which part or all of H bonded to is substituted with F, particularly a surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group. The blending amount of the fluorine-based surfactant is 1 vinyl chloride resin.
0.01 parts by weight or more and 0.5 parts by weight or less per 100 parts by weight is sufficient, and the preferable range of the compounding amount is 0.02 to 0.1 part by weight.
2 parts by weight.

Examples of the lubricant or heat stabilizer include chelators such as fatty acid lubricants, fatty acid amide lubricants, ester lubricants, polyethylene wax, liquid paraffin, and organic phosphite compounds which are generally used for agricultural films; And β-diketone compounds. As the β-diketone compound, dibenzoylmethane,
Preferred are methoxybenzoyl benzoylmethane, chlorobenzoyl benzoylmethane, palmitylbenzoylmethane and the like. The amount of these lubricants and heat stabilizers is
In the range from 0.01 to 2.0 parts by weight, in particular from 0.04 to 1.
0 parts by weight is preferred.

The ultraviolet absorber may be any one which is usually blended in an agricultural vinyl chloride film, and includes various ultraviolet absorbers such as benzotriazole, benzophenone, salicylate, hydroquinone and cyanoacrylate. Can be Specifically,
No. 38143, column 7, line 27 to column 9, line 34;
An ultraviolet absorber described in JP-B-62-53543, column 7, lines 13 to 36. The ultraviolet absorbers can be used alone or in combination of two or more. Benzotriazole-based UV absorbers and benzophenone-based UV absorbers are particularly preferred. The compounding amount is in the range of 0.01 to 3.0 parts by weight, particularly preferably 0.02 to 2.0 parts by weight, per 100 parts by weight of the vinyl chloride resin.

In the present invention, an inorganic substance that absorbs in the infrared region can be blended for the purpose of improving heat retention. Specifically, the following are mentioned. Magnesium carbonate,
Magnesium silicate (talc), silicon oxide, aluminum oxide, barium sulfate, calcium sulfate, magnesium hydroxide, aluminum hydroxide, aluminum hydroxide, calcium hydroxide, metal phosphate, hydrotalcites (hydrous or anhydrous) Aluminum / magnesium basic carbonate); aluminum / zinc basic carbonate lithium carbonate-aluminum hydroxide inclusion compound, and the like. Of these, aluminum hydroxide, magnesium hydroxide,
Silicon oxide, magnesium carbonate, and hydrotalcites are particularly preferable because they do not decrease the transparency of the film. One or more of these inorganic substances can be added, and the compounding amount is preferably in the range of 0.5 to 10 parts by weight, particularly preferably in the range of 2 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin. .

As the compound which can be used as an antioxidant, phenolic and sulfuric antioxidants can be used. Specifically, 2,6-di-butyl-4-methylphenol-
2,2'-methylenebis (6-tert-butyl-4-
Ethylphenol), dilaurylthiodipropionate and the like. These antioxidants can be used alone or in combination of two or more.

Compounds that can be used as a stabilizing aid include triphenyl phosphite, dioctyl phenyl phosphite, tris (nonylphenyl) phosphite, diphenyl indecyl phosphite, trilauryl trithio phosphite, diphenyl acid phosphite and the like. Can be given. These stabilizing aids can be used alone or in combination of two or more.

Examples of the antistatic agent include polyoxyethylene alkylamine, polyglycol ether, p-
And sodium styrenesulfonate. As the fungicide and the anti-algal agent, various compounds generally used in agricultural vinyl chloride films can be used.
Examples thereof include organic nitrogen compounds, and specific examples thereof include imidazole derivatives, anilide derivatives, urea derivatives, ammonium derivatives, triazine derivatives, and phthalimide derivatives. Examples of usable coloring agents include phthalocyanine blue, phthalocyanine green,
Hansa Yellow, Alizarin Lake, titanium oxide, zinc white, permanent red, quinacridone, carbon black and the like can be mentioned. These colorants can be used alone or in combination of two or more.

The above various resin additives can be selected in a range that does not deteriorate the properties of the film, usually in a range of 5 parts by weight or less based on 100 parts by weight of the vinyl chloride resin.
To blend the resin additives into the vinyl chloride resin, weigh each required amount, and use a ribbon blender, Banbury mixer,
What is necessary is just to use a super mixer and other conventionally known compounding machines and mixers.

The resin composition thus obtained can be formed into a film by a method known per se, for example, a melt extrusion molding method (including a T-die method and an inflation method),
A known method such as a calendering method or a solution casting method may be used. The thickness of the film is 0.03-
0.3 mm range, preferably 0.05-0.2 mm
It is preferable to set it in the range.

When the surface-treated vinyl chloride-based resin fibers are sandwiched between two vinyl chloride-based resin films, the arrangement of the fibers is linear, lattice-shaped in various shapes, and Japanese Patent Publication No.
Any of random shapes as described in Japanese Patent No. 25191 may be used. As a method of sandwiching the fiber and the film,
What is necessary is just to employ | adopt the well-known method conventionally known. For example, a method of heat-pressing the film prepared above on both sides of the fiber, or a method of sandwiching via an adhesive, or while extruding a resin composition with an extruder, the film still in a molten state is coated on both sides of the fiber. Or a method of laminating and pressing one side at a time.

[0037]

Industrial Applicability The vinyl chloride resin film for agriculture of the present invention is excellent in durability without deterioration of physical properties or change in appearance, and therefore is used for coating for houses (greenhouses), for tunnels, etc. It can also be used for skylights, doorways, wives, etc., and is extremely valuable as an agricultural covering.

[0038]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. Examples 1 to 5 and Comparative Examples 1 and 2 (1) Production of vinyl chloride resin film Polyvinyl chloride (degree of polymerization = 1300) 100 parts by weight Dioctyl phthalate 45 parts by weight Tricresyl phosphate 5 parts by weight Epoxy resin (trade name) "EP-828") 1 part by weight Ba-Zn liquid stabilizer 1 part by weight Barium stearate 0.2 part by weight Zinc stearate 0.4 part by weight Sorbitan monopalmitate 1.5 parts by weight β-diketone compound (dibenzoyl) (Methane) 0.1 part by weight Benzotriazole-based UV absorber 0.05 part by weight (trade name "TINUVIN-P") Fluorine-based surfactant (trade name "Unidyne DS-401") 0.2 part by weight After weighing the resin raw materials and the resin additives, stirring and mixing them with a super mixer for 10 minutes, 165 ° C.
The mixture was kneaded on a heated roll, and a transparent vinyl chloride resin film having a thickness of 0.10 mm was produced using an L-type calender.

(2) Surface treatment As the vinyl chloride resin fiber, Tevilon (polyvinyl chloride synthetic fiber, multifilament yarn 1) manufactured by Teijin Limited.
(200 denier / 240 filaments) are treated with a surface treatment agent of the type shown in Table 1 by a roll coating method. In the case of an emulsion, the emulsion is kept in a warm air at 90 ° C. for 1 minute to perform a surface treatment on the fiber. did.

(3) Production of Agricultural Film Surface-treated fibers are arranged between two vinyl chloride resin films in a grid pattern with a fiber spacing of 3 cm.
Under the heating condition of 50 ° C, heat-bonded with a laminator,
An agricultural film was created. The obtained film was subjected to a weather resistance test and an impact test.

(Weather Resistance Test) The test film was exposed outdoors to a closed type house at 45 ° on the south side, and the weather resistance of the film portion in contact with the fibers was evaluated by visual observation. The evaluation criteria for the weather resistance are as follows. 5 points: no change 4 points: slight brown spots 3 points: brown spots 2 points: many brown spots 1 point: overall browning In addition, outdoor exposure was carried out on a test field in Mie Prefecture at H6.6-H.
Tested to 6.12. (Impact test) The impact strength of the above test film was measured with a puncture tester manufactured by Toyo Seiki Co., Ltd., and the residual strength was calculated by the following equation. The measurement temperature is −5 ° C.
However, the film was set so that the dart hit the yarn. Residual strength (%) = (strength after outdoor exposure) / (strength before outdoor exposure) x 100

[0042]

[Table 1]

The notes in Table 1 mean the following: * 1 TSF451: dimethyl silicone oil manufactured by Toshiba Silicone Co., Ltd. TSF484: methyl hydrogen silicone oil manufactured by Toshiba Silicone Co., Ltd. TSF4706: amino-modified silicone oil manufactured by Toshiba Silicone Co., Ltd. TEX103: dimethyl silicone oil emulsion manufactured by Toshiba Silicone Co., Ltd. TSW831: Methyl hydrogen silicone oil emulsion manufactured by Toshiba Silicone Co., Ltd. A-104: Acrylic emulsion manufactured by Toagosei Co., Ltd.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kanako Oyama 2 Oike, Iwatsuka-cho, Nakamura-ku, Nagoya-shi, Aichi Prefecture Mitsubishi Chemical MKV Corporation Nagoya Office (72) Inventor Atsushi Obayashi 2 Oiketsu, Iwatsuka-cho, Nakamura-ku, Nagoya-shi, Aichi Prefecture Address Mitsubishi Chemical MKV Corporation Nagoya Office (56) References JP-A-8-174772 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01G 9/14 A01G 13/02 B32B 5/08 B32B 27/12 B32B 27/30

Claims (3)

(57) [Claims] [Claim 1] Between two vinyl chloride resin films,
A vinyl chloride resin film for agriculture, comprising a group of yarns made of vinyl chloride resin fibers surface-treated with silicone oil. 2. The agricultural polyvinyl chloride resin film according to claim 1, wherein the silicone oil contains solid fine particles. 3. The agricultural vinyl chloride resin film according to claim 1, wherein the amount of the silicone oil attached is 0.5 to 30% based on the weight of the vinyl chloride resin fiber.