JP3094885B2 - 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 resin film for agricultural use which has good weather resistance and is composited with a vinyl chloride resin fiber.

[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 tear, a polyester resin thread or strip-shaped tape is randomly crossed to form a lattice, and the lattice-bonded material is laminated with a polyvinyl chloride film to form a film ( Tokiko 40-2519
1, JP-A-2-100621, JP-A-6-62682)
Has been proposed. However, although these films are effective in preventing tearing, when exposed outdoors for a long time as a coating material, they cause browning and deterioration of the films, making it difficult to use them substantially for a long period of time.

[0003]

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 weather resistance and does not cause browning deterioration even when extended for a long period of time.

[0004]

Means for Solving the Problems The present inventors have solved the above-mentioned problems by subjecting a vinyl chloride resin fiber to a surface treatment comprising a specific substance and using a specific compound in combination with the vinyl chloride resin film. It was done. Thus, the gist of the present invention is that (A) at least one compound selected from metal salts of organic phosphoric acid partial esters represented by the general formulas [I] and / or [II]; Formula [II
I] with a hindered amine compound containing at least one structural unit per molecule in a vinyl chloride resin 10
0.02 parts by weight based on the total amount of (A) and (B)
-8 parts by weight, and between the two vinyl chloride resin films blended in a weight ratio of (A) to (B) of 15: 1 to 1:15, the water-soluble polymer or Agricultural vinyl chloride resin films in which a group of yarns composed of vinyl chloride resin fibers surface-treated with an acrylic resin containing at least one hydroxyl group in a molecule (chain) are sandwiched.

[0005]

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 1700.

An alkyl group having 1 to 22 carbon atoms, an aryl group, and an aralkyl group constituting the metal salt of an organic phosphoric acid partial ester represented by the general formula (I) or (II) which is the component (A) used in the present invention. Examples of the hydrocarbon group containing an alkylaryl group or an ether bond include the following. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, sec-butyl group, tert-butyl group, n-amyl group, neopentyl group, isoamyl group, hexyl group, heptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group , Decyl, lauryl, tridecyl, 1-octadecyl, cyclopentyl, cyclohexyl, cyclooctyl, 4-methylcyclohexyl and the like.

Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group, a p-phenethyl group and an α-phenylpropyl group. Examples of the alkylaryl group include a tolyl group, a xylyl group, an ethylphenyl group, a butylphenyl group, a tert-butylphenyl group, an octylphenyl group, a nonylphenyl group, and a 2,4-di-tert-butylphenyl group. be able to.

Examples of the hydrocarbon group containing an ether bond include a furfuryl group, a tetrahydrofurfuryl group, a 5-methylfurfuryl group, an α-methylfurfuryl group, and a methylcellosolve residue (an ether obtained by removing a hydroxyl group from the above cellosolve). A hydrocarbon group containing a bond, the same applies hereinafter), ethyl cellosolve residue, isopropyl cellosolve residue, butyl cellosolve residue, isobutyl cellosolve residue, hexyl cellosolve residue, cyclohexyl cellosolve residue, phenyl cellosolve residue, methyl carbitol Residue (refers to a hydrocarbon containing an ether bond obtained by removing a hydroxyl group from the carbitol, the same applies hereinafter), ethyl carbitol residue, isopropyl carbitol residue, butyl carbitol residue, isobutyl carbitol residue, triethylene Glycol monomethyl A Le residues (refers to a hydrocarbon group containing an ether bond other than a hydroxyl group from the ether, the same below), triethylene glycol monoethyl ether residues, triethylene glycol monobutyl ether residue,
2,3-dimethoxy-n-propyl group, 2,2'-diethoxyisopropyl group, 3-ethoxy-2-propoxy-n-propyl group, nonylphenoxypoly (1-30)
An ethoxyethyl group, a lauroxypoly (1-30) ethoxyethyl group and the like can be mentioned. Also, among the types of metal,
Zinc, calcium and barium are preferred, and zinc is particularly preferred.

[0009] The metal phosphate partial ester metal salts having various substituents as described above can be used alone or in combination of two or more. Examples of the hindered amine compound containing at least one structural unit represented by the general formula (III) in one molecule, which is the component (B) used in the present invention, include JP-A-6-155680, pp. 5-19. The following compounds can be specifically exemplified.

(1) 4-acetoxy-2,2,6,6-
Tetramethylpiperidine (2) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine (3) 4-acryloyloxy-2,2,6,6-tetramethylpiperidine (4) 4- (phenylacetoxy) −2,2,6,6-
Tetramethylpiperidine (5) 4- (phenoxyacetoxy) -2,2,6,6
-Tetramethylpiperidine (6) 4-cyclohexanoyloxy-2,2,6,6
-Tetramethylpiperidine (7) 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (8) 4- (o-chlorobenzoyloxy) -2,2,
6,6-tetramethylpiperidine (9) 4-benzyloxy-2,2,6,6-tetramethylpiperidine (10) 4- (phenylcarbamoyloxy) -2,
2,6,6-tetramethylpiperidine (11) 4- (p-toluenesulfonyloxy) -2,
2,6,6-tetramethylpiperidine (12) 4- (o-toluoyloxy) -2,2,6
6-tetramethylpiperidine (13) 4-isonicotinoyloxy-2,2,6,6
-Tetramethylpiperidine (14) 4- (2-furoyloxy) -2,2,6,6
-Tetramethylpiperidine (15) 4- (β-naphthoyloxy) -2,2,6
6-tetramethylpiperidine (16) bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate (17) bis (2,2,6,6-tetramethyl-4-piperidyl) malonate (18) Bis (2,2,6,6-tetramethyl-4-piperidyl) adipate (19) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebagate (20) Bis (2,2,6, 6-tetramethyl-4-piperidyl) fumarate (21) bis (2,2,6,6-tetramethyl-4-piperidyl) hexahydroterephthalate (22) bis (2,2,6,6-tetramethyl-4) -Piperidyl) terephthalate (23) tris (2,2,6,6-tetramethyl-4-)
Piperidyl) benzene-1,3,5-tricarboxylate (24) tris (2,2,6,6-tetramethyl-4-
Piperidyl) triazine-2,4,6-tricarboxylate (25) tris (2,2,6,6-tetramethyl-4-
Piperidyl) nitrotriacetate (26) tris (2,2,6,6-tetramethyl-4-
Piperidyl) butane-1,2,3-tricarboxylate (27) tetrakis (2,2,6,6-tetramethyl-
4-piperidylnopropane-1,1,2,3-tetracarboxylate (28) tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) butane-1,2,3,4-tetracarboxylate (29) tris (2,2,6,6-tetramethyl-4-
Piperidyl) -2-acetoxypropane-1,2,3-
Tricarboxylate (30) Tris (2,2,6,6-tetramethyl-4-
Piperidyl) -2-hydroxypropane-1,2,3-
Tricarboxylate (31) 1,2,3,4-tetra (4-carbonyloxy-2,2,6,6-tetramethylpiperidine) -butane (32) tri- (4-acetoxy-2,2,6 , 6-Tetramethylpiperidine) -amine (33) Tris (2,2,6,6-tetramethyl-4-
(Piperidine) phosphite (34) 1,3,8-triaza-7,7,9,9-tetramethyl-2,4-dioxo-spiro [4,5] decane (35) tetrakis (2,2,6, 6-tetramethyl-
4-piperidyl) propane-1,1,3,3-tetracarboxylate

(36) "Tinuvi" manufactured by Ciba-Geigy
n 622 "

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(37) "Tinuvi" manufactured by Ciba-Geigy
n 144 "

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(38) "CHIMASSORB 944" manufactured by Chisamo Chimica Organica S.P.A.

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The compounding amount of the organic phosphoric acid partial ester metal salt as the component (A) and the hindered amine compound as the component (B) is based on 100 parts by weight of the vinyl chloride resin.
The total amount of (A) and (B) is in the range of 0.02 to 8 parts by weight. When the total amount of (A) and (B) is less than this range, the weather resistance of the vinyl chloride resin film is not sufficiently excellent, and when the total amount is large, it is added after forming the film. However, there is a problem that the gas spouts out, which is not preferable. Of the above ranges, a range of 0.1 to 3 parts by weight is particularly preferred. The mixing ratio of the component (A) and the component (B) is such that the weight ratio of the component (A) to the component (B) is in the range of 15: 1 to 1:15. Within this range, an effect of preventing browning deterioration is exhibited. It is particularly preferable that the mixing ratio be in the range of 10: 1 to 1:10.

Further, the vinyl chloride resin film composition according to the present invention contains a plasticizer, an antifogging agent, an antifog agent, a lubricant, a heat stabilizer, an ultraviolet absorber, an inorganic substance, an antioxidant, and a stabilizing aid. And various additives such as 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
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 based on 100 parts by weight of the vinyl chloride resin. In addition, epoxy plasticizer,
Organic phosphate esters and the like can be mentioned. Epoxy plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil and epoxy resins.
The addition amount of these epoxy plasticizers is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin.
Parts by weight. The compounding amount of the organic phosphate plasticizer is 1 to 100 parts by weight of the vinyl chloride resin.
A range of 10 parts by weight, especially 2 to 8 parts by weight, is suitable. As the antifogging agent, nonionic surfactants are preferable, and polyoxyethylene ethers, polyoxyethylene alkylaryl ethers, ether-type ones such as polyoxyethylene polyoxypropylene ether, and fatty acids with polyhydric alcohols Examples thereof include an ester type of a partially esterified product, and an ether ester type such as polyoxyethylene ether of glycerin ester and polyoxyl ethylene ether of sorbitan ester. Hereinafter, suitable nonionic surfactants will be exemplified.

(A) 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 antimist agent include a fluorine-based surfactant. Specifically, it is a surfactant in which a part or all of a normal surfactant is substituted with F instead of H bonded to C of a hydrophobic group, and particularly contains a perfluoroalkyl group or a perfluoroalkenyl group. It is a surfactant. 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 of those usually blended in agricultural vinyl chloride films, 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.
0.5 to 10 parts by weight per part by weight, especially 2 to 1
A range of 0 parts by weight is preferred. As the compounds usable as antioxidants, phenolic and sulfuric antioxidants can be used, and 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 isodecyl 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. In order to form the resin composition thus obtained into a film, a method known per se, for example, a melt extrusion molding method (including a T-die method and an inflation method), a calendar molding method, a solution casting method, and the like. May be used according to the conventionally known method. The thickness of the film is in the range of 0.03 to 0.3 mm, preferably 0.1 to 0.3 mm.
It is preferable to set it in the range of 0.5 to 0.2 mm.

The vinyl chloride resin fibers used in the present invention are:
Dry spinning, melt spinning of the above-mentioned vinyl chloride resin
Also, the fiber may be formed by a method such as a wet spinning method.
More specifically, the spinning method manufactured by the dry spinning method is particularly useful.
Robil by Bill, Tevilon by Teijin Limited is preferred.
You. The thickness of the fiber is 300 denier to 3
000 denier, especially 600 denier to 25
00 denier is preferred. Less than 300 denier
Insufficient fiber strength prevents the propagation of tears
On the other hand, if it exceeds 3000 denier, the fiber strength becomes strong.
However, the transmittance is undesirably reduced. Fiber diameter
Is in the range of 5 μm to 30 μm, particularly 10 μm to 40 μm.
m is preferred. Fiber density is 3g / m^Two~ 30g / m
^TwoBut especially 5 g / m^Two~ 25g / m ^TwoIs preferred. 3
g / m^TwoIf it is less than it can not prevent the occurrence of tears,
30g / m^TwoExceeding this is undesirable because the transmittance will decrease.
No.

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. Examples of the water-soluble polymer for surface treatment include polyvinyl alcohol (hereinafter referred to as PVA), polyethylene oxide, sodium polyacrylate, such as water-soluble celluloses such as carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, and ethylcellulose;
Alternatively, viscose, for example, soluble starch such as carboxymethyl starch, dialdehyde starch, potato starch, wheat starch, corn starch and the like can be mentioned, and PVA and water-soluble celluloses are particularly preferred. These water-soluble polymers may be used alone or in combination of two or more.

In order to surface-treat such a water-soluble polymer on a vinyl chloride resin fiber, it is preferable to dissolve the water-soluble polymer in an aqueous dispersion and to treat it. As the dispersion medium, water or warm water, or a mixture of water and an organic solvent such as alcohol and ketone can be used. The acrylic resin containing at least one hydroxyl group in a molecule (chain) for surface treatment refers to 5 to 40% by weight of a hydroxyalkyl (meth) acrylate, and one or two or more hydroxyalkyl (meth) acrylates in the molecule. A polymer obtained by copolymerizing a monomer mixture containing 0.5 to 20% by weight of an α, β-unsaturated carboxylic acid compound containing a carboxyl group and another vinyl monomer copolymerizable therewith is used. Say.

Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-
Examples thereof include hydroxybutyl methacrylate, 2-hydroxypentyl acrylate, 2-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, and 6-hydroxyhexyl methacrylate.

When the ratio of the hydroxyalkyl (meth) acrylate in the acrylic resin is less than 5% by weight, the solubility in an organic solvent and the adhesion to a vinyl chloride resin fiber can be sufficiently exhibited. And, on the other hand, 40% by weight
If it is larger, the cost is high, and the effect obtained is not so large as compared with the cost increase. Α, β- containing one or more carboxyl groups in the molecule
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, aconitic acid, fumaric acid, crotonic acid, itaconic acid and the like. When these compounds are used in combination with the hydroxyalkyl (meth) acrylate, the adhesion between the acrylic resin and the vinyl chloride resin fiber is improved. The use amount of these is preferably 0.5 to 20% by weight. If it is more than this, the vinyl chloride resin film and the acrylic resin are fused and adversely affect weather resistance, which is not preferable. Examples of the other vinyl monomers copolymerizable with the hydroxyalkyl (meth) acrylate and the α, β-unsaturated carboxylic acid include (meth) acrylic acid alkyl esters or a mixture thereof with alkenylbenzene. .

Examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-acrylate. Ethylhexyl ester, decyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid
Examples thereof include n-propyl ester, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and decyl methacrylate, and are generally acrylic having 1 to 20 carbon atoms in the alkyl group. Acid alkyl esters and / or alkyl esters of methacrylic acid having 1 to 20 carbon atoms in the alkyl group are used.

The alkenylbenzene used in the present invention includes, for example, styrene, α-methylstyrene, vinyltoluene and the like. When using a monomer composed of a mixture of such an alkenylbenzene and an alkyl (meth) acrylate, the amount of the α, β-ethylenically unsaturated carboxylic acid varies depending on the amount of the monomer used. Use ratio of alkyl acrylate of 10
% By weight or more. In particular, the acrylic resin of the present invention preferably contains 40 to 60% by weight of a monomer composed of the above-mentioned alkyl (meth) acrylate and a mixture of this and alkenylbenzene.

When such an acrylic resin is subjected to surface treatment on a vinyl chloride resin fiber, it is possible to mix another resin compatible with the acrylic resin for the purpose of improving the adhesion to the fiber. is there. As the other resin, a vinylidene fluoride resin, an acrylic resin having a perfluoroalkyl group in a side chain, a cellulose acetate butyrate resin, a silicone resin, and the like are particularly effective.

Such an acrylic resin is prepared by combining a predetermined amount of a monomer mixture, charging it together with an organic solvent in a polymerization vessel, adding a polymerization initiator and, if necessary, a molecular weight regulator, heating with stirring, and polymerizing. Good. The polymerization method can be produced by a conventionally known polymerization method, and the charging method of the monomer may be a batch method or a continuous feeding method. Alternatively, a system may be used in which a part is first polymerized and then the remaining part is continuously fed. The monomer to be continuously fed may be as it is,
A system in which water and a surfactant are used to feed a monomer dispersion is extremely suitable. Also, acrylic resin,
The monomer mixture may be used as an aqueous emulsion polymerized in an aqueous medium in the presence of a surfactant. Even if the obtained aqueous emulsion is used as it is,
It may be diluted by adding a liquid dispersion medium, or a polymer produced by the above-mentioned polymerization may be separately collected and redispersed in a liquid dispersion medium to form an aqueous emulsion.

The surfactant may be any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant. These may be used alone or in combination. However, when an inorganic substance is blended, there is a limitation depending on the type. That is, a combination of a silica sol and a cationic surfactant, which are generally charged to an anionic charge in an aqueous solution, and a combination of an alumina sol and an anionic surfactant, generally charged to a positive charge in an aqueous solution, should be avoided. These combinations are liable to cause the sol to form a sol or agglomerate and separate the aqueous emulsion, making surface treatment difficult. These surfactants are used in an amount of 0.1 to 10% by weight based on the total amount of the charged monomers.
Used in the range.

Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate; and organic peroxides such as acetyl peroxide and benzoyl peroxide. These are used in an amount of 0.1 to the total amount of the charged monomers.
It is used in the range of 1 to 10% by weight. As the inorganic colloid sol, for example, silica, alumina, water-insoluble lithium silicate, iron hydroxide, tin hydroxide, titanium oxide, inorganic aqueous colloid particles such as barium sulfate, by various methods, dispersed in water or a hydrophilic medium. And an aqueous sol. Among them, silica sol and alumina sol are preferable. These may be used alone or in combination.
The average particle diameter of the inorganic colloid sol used is 5
Those having a range of from to 1000 nm are preferable. Within this range, two or more types of colloid sols having different average particle sizes may be used in combination. If the average particle diameter exceeds 1000 nm, the appearance tends to be white and devitrified, and
If less than the above, the stability of the inorganic colloid sol may be lacking, which is not preferable.

It is important that the amount of the inorganic colloid sol be less than 0.5 in terms of the weight ratio of the solid content to the acrylic resin. When used as an aqueous emulsion, it is preferable to further incorporate a crosslinking agent. That is, the acrylic resin is cross-linked by the cross-linking agent, and the adhesion can be improved. Examples of the cross-linking agent include phenolic resins, amino resins, amine compounds, aziridine compounds, azo compounds, isocyanate compounds, epoxy compounds, silane compounds, and the like. Particularly, amine compounds, aziridine compounds And epoxy compounds.

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 resin formed by the reaction of epichlorohydrin with the reaction product of bisphenol A or bisphenol F with epichlorohydrin, 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 an amount of 0.1 to 30% by weight based on the solid content of the acrylic resin. 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. The acrylic resin surface-treated coating film formed on the vinyl chloride-based resin fiber is preferably treated by dissolving the acrylic resin in an organic solvent.

The organic solvent for dissolving the acrylic resin may be the same as the solvent used for producing the acrylic resin. Specifically, alcohols are desirable, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, tert-amyl alcohol, n-hexyl alcohol And cyclohexanol. In addition to the above alcohols, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, hexane, toluene, xylene, chloroform and the like can also be used. These may be one kind or a mixture of two or more kinds.

The various surface-treated resins may further contain a small amount of an acid or alkali defoaming agent, a surfactant, an antistatic agent, an antioxidant, a fungicide, an antialgal agent, an alkaline paste, if necessary. Known additives such as various oils and leveling agents can be mixed. As a method for surface-treating these water-soluble polymers or acrylic resins containing at least one hydroxyl group in a molecule (chain) to vinyl chloride resin fibers,
Any known coating method such as a roll coating method, a gravure coating method, a reverse coating method, and a dip coating method may be used. As a method for drying the applied resin, 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 in the range of 50 to 250C, preferably 70 to 200C. Adhesion amount of the vinyl chloride resin fiber surface treatment resin, per unit surface area 0.2 to 10 g / m ^2, in particular in the range of 0.4~7g / m ² is preferred. 0.2 adhesion amount to vinyl chloride resin fiber
If it is less than g / m ² , the weather resistance will not be sufficiently excellent, while if it is more than 10 g / m ² , the fibers will be too strong and the initial physical properties of the film holding the fibers will be reduced. Not preferred.

When the surface-treated vinyl chloride-based resin fibers are sandwiched between two vinyl chloride-based resin films, the arrangement of the fibers may be linear, lattice-shaped in various shapes, or specially designed.
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.

[0044]

EFFECT OF THE INVENTION The agricultural polyvinyl chloride resin film of the present invention is free from browning deterioration and has excellent weather resistance.
It can be used not only for coating for houses (greenhouses) and for tunnels, but also for the side of houses, skylights, doorways, wives, etc., and is extremely valuable as an agricultural coating material.

[0045]

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 19, Comparative Examples 1 to 17 (1) Production of vinyl chloride resin film 100 parts by weight of polyvinyl chloride (polymerization degree = 1300) 45 parts by weight of dioctyl phthalate 5 parts by weight of tricresyl phosphate Epoxy resin (trade name) "EP-828") 1 part by weight Ba-Zn liquid stabilizer 2 parts 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 0.5 parts by weight β-diketone compound 0.1 parts by weight (dibenzoylmethane) Benzotriazole UV absorber 0.05 parts by weight (trade name “TINUVIN-P”) Fluorine surfactant 0.2 parts by weight (trade name) "Unidyne DS-401" manufactured by Daikin Industries, Ltd.) The above-mentioned resin raw materials are used as a basic composition.
The components (A) and (B) of the types shown in Tables, Tables 2 and 4, were blended at the blending ratios shown in the same table. After stirring and mixing these with a super mixer for 10 minutes,
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) Preparation of Surface Treatment Agent Water-Soluble Polymer The type and amount of water-soluble polymer shown in Table 1 were dissolved in water or warm water to obtain a surface treatment agent. Acrylic resin i) The composition shown in Table 2 (excluding isopropyl alcohol) was compounded in a polymerization vessel, and the mixture was heated at 80 ° C. under a nitrogen gas stream at 80 ° C.
The polymerization reaction was performed for 0 hours. To the obtained copolymer solution, isopropyl alcohol was added in the amount shown in Table 2 to obtain a surface treating agent. ii) Water-based emulsion A four-necked flask was charged with 2 parts by weight of polyoxyethylene lauryl ether and 80 parts by weight of water and heated to 60 ° C. under a stream of nitrogen gas.
Then, 100 parts by weight of a mixture of each monomer shown in Table 3 was added dropwise over 3 hours. The reaction temperature is maintained in the range of 60 to 70 ° C., and after the completion of the dropwise addition, the temperature is maintained in the same temperature range for 2 hours, then cooled, neutralized with ammonia water, and the hydrophobic acrylic resin aqueous emulsion (resin A to
E) was obtained. To the resins A to E obtained, inorganic colloid sols, liquid dispersants and crosslinking agents of the types and amounts shown in Table 4 were added to obtain surface treatment agents.

(3) Surface Treatment Teflon (polyvinyl chloride synthetic fiber filament yarn 1200 denier / 240 filament) manufactured by Teijin Limited as a vinyl chloride resin fiber is roll-coated with the surface treatment agent prepared in the above (2). Water-soluble polymer for 1 minute in a hot air at 70 ° C. for i), 10 seconds in a hot air of 120 ° C. for i) acrylic resin, and 90 in an aqueous emulsion for ii). Each of them was kept in warm air at a temperature of 1 ° C. for 1 minute, and the solvent was scattered to form a coating film.

(4) Production of Agricultural Film The surface-treated fiber is placed between two vinyl chloride resin films in parallel with the film every 3 cm, and is thermally bonded by a laminator under a heating condition of 150 ° C. An agricultural film was created. However, Comparative Examples 1 and 2 were thermally bonded without inserting a vinyl chloride resin fiber. The resulting film was subjected to an impact test and a weather resistance test.

(Weather Resistance Test) The test film was exposed outdoors to a closed house at 45 ° on the south side, and the weather resistance of the film was evaluated by visual observation. The evaluation criteria for the weather resistance are as follows. 5 points: no change 4 points: slightly 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 the ash fall area, H5.3 to H
Tested to 5.9. (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. Residual strength (%) = (strength after outdoor exposure) / (strength before outdoor exposure) x 100

[0050]

[Table 1]

The notes in Table 1 mean the following. * 1 Zinc stearyl phosphate * 2 1,2,3,4-tetra (4-carbonyloxy-2,2,6,6-tetramethylpiperidine) -butane * 3 SM-15: manufactured by Shin-Etsu Chemical Co., Ltd. Metros SM-15
Methyl cellulose 90SH-400 having a methoxy group of 27.5 to 31.5%: Metroose 90SH-4 manufactured by Shin-Etsu Chemical Co., Ltd.
00 methoxy group 19 to 24%, hydroxypropoxy group 4 to 12% NL-05: Gohsenol N manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
L-05 PVA GL-05 having a saponification degree mol% of 98.5 or more: Gohsenol G manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
L-05 PVA KL-05 having a saponification degree mol% of 86.5 to 89.0: Gohsenol K manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
L-05 PVA GH-17 having a saponification degree of mol% of 78.5 to 81.5: Gohsenol G manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
H-17 PVA with saponification degree mol% of 86.5 to 90.0 * 4 Breakdown of oil agent Smoothing agent (“Suntex T-190” manufactured by Goyo Chemical Co., Ltd.) 0.2 parts by weight Antistatic agent (manufactured by Matsumoto Yushi Co., Ltd.) "Fcol # 214") 0.15 parts by weight Defoamer ("Nopco # 8034" manufactured by San Nopco) 0.05 parts by weight

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

──────────────────────────────────────────────────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: Nagoya Office, Mitsubishi Chemical MKV Co., Ltd. (56) References JP-A-6-134939 (JP, A) JP-A-9-216316 (JP, A) JP-A 8-174772 (JP, A) 8-16989 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 A01G 9/14 A01G 13/02

Claims (7)

(57) [Claims] 1. A compound represented by (A) at least one compound selected from metal salts of organic phosphoric acid partial esters represented by the general formulas (I) and / or [II]; and (B) a compound represented by the general formula [III] A hindered amine compound containing one or more structural units per molecule in a molecule, with respect to 100 parts by weight of a vinyl chloride resin, in a total amount of 0.02 to 8 parts by weight of (A) and (B), and , (A) to (B) in a weight ratio of 15: 1 to 1:15, between two vinyl chloride resin films, between a water-soluble polymer or a molecule (chain). A vinyl chloride resin film for agricultural use, comprising a group of yarns made of vinyl chloride resin fibers surface-treated with an acrylic resin containing at least one hydroxyl group. Embedded image (Wherein M is zinc, calcium, barium, magnesium or strontium, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each an alkyl group having 1 to 22 carbon atoms, an aryl group, an aralkyl group, an alkyl group) It means an aryl group or a hydrocarbon group containing an ether bond, respectively.) (Wherein, R ^{6 to} R ⁹ are an alkyl group having 1 to 4 carbon atoms, R ¹⁰
Represents hydrogen or an alkyl group having 1 to 4 carbon atoms. ) 2. The vinyl chloride resin film for agricultural use according to claim 1, wherein the water-soluble polymer is polyvinyl alcohol and / or a water-soluble cellulose. 3. An acrylic resin comprising 5 to 40% by weight of hydroxyalkyl (meth) acrylate, 1 or 2
A copolymer obtained by polymerizing a monomer mixture containing 0.5 to 20% by weight of an α, β unsaturated carboxylic acid containing at least one carboxyl group and another vinyl monomer copolymerizable therewith. The agricultural polyvinyl chloride resin film according to claim 1, which is a coalesced product. 4. As another vinyl monomer copolymerizable in the monomer mixture, an alkyl (meth) acrylate or a mixture thereof with alkenylbenzene is used in an amount of 40 to 6%.
The vinyl chloride resin film for agricultural use according to claim 3, which contains 0% by weight. 5. The acrylic resin according to claim 1, wherein the acrylic resin is an aqueous emulsion obtained by polymerizing a monomer mixture in an aqueous medium in the presence of a surfactant. Agricultural vinyl chloride resin film. 6. The vinyl chloride resin film for agricultural use according to claim 5, wherein the aqueous emulsion contains an inorganic colloid sol. 7. The adhesion amount of a water-soluble polymer or an acrylic resin containing at least one hydroxyl group in a molecule (chain) is 0.2% per unit surface area of a vinyl chloride resin fiber.
Agricultural vinyl chloride resin film according to any one of claims 1 to 6 is ~10.0g / m ^2.