JPH0230529A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PURPOSE:To enhance a durability by applying a film mainly composed of a silane compound, an acrylic resin, and a hindered amine compound on either or both surfaces of a soft vinyl chloride resin film containing an organic phosphoric ester and/or an organic phosphoric metallic salt. CONSTITUTION:On either or both surfaces of a soft vinyl chloride resin film containing an organic phosphoric ester and/or an organic phosphoric metallic salt, a film mainly composed of a silane compound A having hydrolyzable groups directly bonding with silicon atoms, an acrylic resin B obtained by polymerizing a monomer selected from among alkyl esters of acrylic acid or methacrylic acid [hereinafter, this is expressed as (meta)acrylic alkyl esters] or a mixture of this monomer and an alkenyl benzene monomer and a copolymerizable alpha,beta-ethylene unsatd. monomer, and a hindered amine compound C is formed under a thermal treatment. The acrylic resin can be obtained by polymerizing an alkyl ester monomer of acrylic acid or methacrylic acid in a single form or in a mixed form with an alkenyl benzene monomer and a copolymerizable alpha,beta-ethylene unsatd. monomer.

Description

[Detailed description of the invention] "Industrial application field" The present invention relates to an agricultural vinyl chloride resin film.

More specifically, the present invention relates to an agricultural vinyl chloride resin film that prevents undesirable deterioration phenomena such as discoloration, embrittlement, and reduction in dust resistance caused when stretched outdoors, and has improved durability.

"Prior Art" Conventionally, in order to prevent photodeterioration of vinyl chloride resin films used as covering materials for agricultural greenhouses or tunnels due to sunlight, UV absorbers and/or Or add and blend antioxidants,
Film-forming techniques are widely employed (for example, see Japanese Patent Publication No. 4837459, Japanese Patent Publication No. 53-47383, etc.). According to this method, harmful light rays that promote film deterioration are gradually absorbed and weakened as they pass through the film from the incident side to the opposite side. In this case, the side of the film on which the light rays are incident is damaged by harmful rays, resulting in the drawback that the weather resistance of the film cannot be sufficiently improved.

On the other hand, based on conventional experience, the soft vinyl chloride resin film used for agricultural purposes has been stretched to a certain extent depending on the region and place where it is used.
After many years, the dust-proofing properties of the surfaces located on the outside of the house or tunnel deteriorate significantly and they become unusable.

As a method to eliminate the above drawbacks,
Publication No. 1987-31195, Japanese Patent Publication No. 1983-31195
As described in Japanese Patent Publication No. 99237, Japanese Patent Publication No. 5699665, etc., a coating of a specific acrylic resin,
There is a method of forming it on one or both sides of a vinyl chloride resin film as a substrate. Further, JP-A-51-70282 describes a method of forming a coating of an acrylic resin of a specific composition containing an ultraviolet absorber on the surface of a film of a substrate. However, since the coating formed on the base film in these methods is mainly made of thermoplastic resin, it
It is difficult to completely prevent the additives contained in the base film from migrating to the surface through the film and being washed away and disappearing, so it is difficult to completely prevent the additives contained in the base film from being transferred to the surface and being washed away. , there was still a problem.

Therefore, in order to further improve the above-mentioned drawbacks,
As described in JP-A-53070, JP-A-5770031, JP-A-57-163568, etc., vinyl chloride-based 0 (at least one surface of a fat film is cured with energy rays using cationic polymerization). However, the epoxy resin composition that is preferably used as a cationic polymerization-based energy ray-curable resin composition according to this method has a coating film formed by this method that deteriorates in weather resistance. It had the disadvantage that it was easily susceptible to damage and could not fully achieve its intended purpose.

"Problems to be Solved by the Invention" The present inventors discovered that undesirable deterioration phenomena such as discoloration, embrittlement, and reduction in dust resistance caused by stretching outdoors are significantly With the aim of providing an agricultural vinyl chloride resin film with improved properties and durability, the present invention was completed as a result of intensive studies.

"Means for Solving the Problems" The above problems can be solved by using the agricultural vinyl chloride resin film according to the present invention. That is,
The essence of the present invention is that one side of a soft vinyl chloride resin film containing a fi phosphate ester and/or a fi IJ phosphate metal salt or a coating mainly composed of a young good amine compound is The present invention relates to an agricultural vinyl chloride resin film formed by heat treatment.

The present invention will be explained in detail below.

In the present invention, the vinyl chloride resin includes not only polyvinyl chloride but also copolymers whose main component is vinyl chloride.

Examples of monomer compounds copolymerizable with vinyl chloride include vinylidene chloride, ethylene, brobylene, acrylonitrile, maleic acid, itaconic acid, acrylic acid, methacrylic acid, and vinyl acetate. These vinyl chloride resins may be produced by any of conventionally known production methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

]20 to 6 parts by weight per 100 parts by weight of the vinyl chloride resin serving as the substrate in order to impart flexibility.
0 parts by weight of plasticizer are incorporated. By controlling the blending amount of the plasticizer within the above range, it is possible to impart excellent flexibility and mechanical properties to the target vinyl chloride resin film.

As a plasticizer, for example, No I+-octyl 7 tallate, No 2-ethylhexyl 7 tallate, Cybennol 7 tallate,
Heptatalic acid derivatives such as talate, diisodecyl 7talate, didodecyl 7talate, and solandecylphthalate; Isophthalic acid derivatives such as nooctyl 7talate; No+1
-Adipic acid derivatives such as butyl anovate and dioctyl acebate; maleic acid derivatives such as di-11-butyl maleate; citric acid derivatives such as tri-1-1-butyl citrate; itaconic acid derivatives such as mobutyl itaconate; butyl oleate Oleic acid derivatives such as oleic acid derivatives such as glycerin monolysyl 7-late; others include epoxidized soybean oil, epoxy resin plasticizers, and the like.

The agricultural vinyl chloride resin film of the present invention is made by blending an organic phosphate ester and/or an organic phosphate metal salt with a vinyl chloride resin described in 2.

Examples of organic phosphoric acid esters include triisopropylphenyl phosphate, indecyl diphenyl phosphate, tricresyl phosphate, tris(isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate,
There are octyl diphenyl phosphate, tricylenyl phosphate, etc. Among them, tricresyl phosphate,
and tricylenyl phosphate are particularly preferred.

Furthermore, a composite material containing an organic phosphate ester as a main component can also be used. For example, a composite of an organic phosphoric acid ester and an organic phosphorous ester can be mentioned. Also included are phosphonate compounds such as diphenylphosphonate. These are generally plasticizers for vinyl chloride resins, and they improve the weather resistance of the film and, together with the formed film, improve the dust resistance. These organic phosphate esters are 1
It can be used as a species or in combination of two or more.

As the phosphoric acid* group salt, general formula [I] or [n
l (wherein M means zinc, calcium, barium, magnesium, cobalt or strontierum; R1, R2 and R3 are each alkyl, aryl,
It means arylalkyl, alkylaryl, or an alkyl group having an ether bond. ) are listed.

Examples of alkyl groups represented by R1, R2 and R'' include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, heptyl, octyl, inoctyl, 2-ethylhexyl,
Decyl, isodecyl, lauryl, tridecyl, CI2~
CI3 mixed alkyl, stearyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-
Examples include methylcyclohexyl group.

Examples of aryl groups include phenyl and naphthyl groups.

Examples of the arylalkyl group include benzyl, β-phenylethyl, α-phenylfurohyl, and β-7enylbrobyl groups.

Examples of alkylaryl groups include tolyl, xylyl,
Examples include ethylphenyl, butylphenyl, tert-butyl 7enyl, octyl 7enyl, in-octyl 7enyl, tertiary octylphenyl, 7yl-7enyl, 2,4-no-tert-butyl phenyl group, and the like.

Examples of the alkyl group having an ether bond include furfuryl, tetrahydrofurfuryl, 5-methylfurfuryl, and a-methylfurfuryl, or methyl, ethyl,
Isopropyl-, butyl-isobutyl-, hexyl-, cyclohexyl-phenyl cellosolve residue; Methyl-,
Ethyl isopropyl, butyl, isobutyl calpitol residues; triethylene glycol monomethyl ether, -monoethyl ether, -monobutyl ether residues;
Glycerin 1,2-dimethyl ether, -1,3-
Nonyl ether, -1-ethyl 2-propyl ether residue; nonyl 7-ethyl 7-oxybolyethoxyethyl, lauroxy polyethoxyethyl residue and the like. Furthermore, among the metals, zinc, calcium and barium are particularly preferred.

Organic phosphate metal salts having various substituents such as Hoshi and ``2'' can be blended singly or in combination of two or more.

The blending amount of the organic phosphate ester and/or the metal phosphate is O to 100 parts by weight of the vinyl chloride resin.
, i% within the range of 15 parts by weight, preferably 0.2%1.
It shall be selected within the range of 0 parts by weight.

If the amount is less than 0.1 part by weight, the weather resistance and dustproof properties of the soft vinyl chloride resin film will not improve.

If the amount is more than 15 parts by weight, the transparency of the film will be extremely poor, which is not preferable. 0 within the above range.
Particularly preferred is 78 parts by weight.

In addition, the vinyl chloride resin contains the plasticizer and Wl.
l) In addition to the phosphoric acid ester and/or the organophosphoric acid metal salt, if necessary, known resin additives that are usually added to synthetic resins for molding, such as lubricants, heat stabilizers, ultraviolet absorbers, Light stabilizers, antioxidants, stabilizing aids, antistatic agents, antistatic agents, antifungal agents, antialgal agents, inorganic fillers, coloring agents, and the like can be blended.

Examples of lubricants, heat stabilizers, and antioxidants that can be incorporated into the film of the present invention include polyethylene wax, bisamide compounds, liquid paraffin, organic heptatoosphite compounds, and β-nokatone compounds.

The above-mentioned various resin additives can be used for 1 m each or in combination of several types.

The amount of the various resin additives added in Section 2 should be within a range that does not deteriorate the properties of the film.
It can be selected within a range of 10 parts by weight or less relative to 0 parts by weight.

In order to blend the plasticizer, organic phosphate ester and/or organic phosphate metal salt, and other resin additives into the vinyl chloride resin that serves as the base of the film, weigh the necessary amount of each,
Any conventional compounding machine or mixer such as a ribbon blender, Banbury mixer, super mixer, etc. may be used. .

The resin composition thus obtained can be formed into a film by a method known per se, such as melt extrusion method (T-
(including Gouy method and inflation method), calendar molding method, solution casting method, etc.

In order to improve the anti-fogging properties and anti-blocking properties of the film, the film formed in this way may be coated with another resin, such as an acrylic resin, on the other film surface, if the coating according to the present invention is on one side of the film. A coating layer made of fluororesin or polyolefin (oil) may be provided.

In the agricultural vinyl chloride resin film of the present invention, a film containing a silane compound, a specific acrylic resin, and a hinged amine compound as main components is formed on one or both sides of the film by heat treatment.

The silane compound used in the present invention has a hydrolyzable group directly bonded to a silicon atom.

Specifically, ami/methyltriethoxysilane, N-β
-aminoethylami7methyltrimethoxysilane, γ-
Aminoalkylalkoxysilanes such as aminopropyltrimethoxysilane, N-(trimethoxysilylpropyl)-ethylenenoamine, N-(nomethoxymethylsilylpropyl)-ethyleneamine; γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxychlorohexyl)ethyltrimethoxysilane, β-(3,
Epoxyalkylalkoxysilanes such as 4-epoxycyclohexyl)ethylmethylnomethoxysilane; Mercaptoalkylalkoxysilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethylnomethoxysilane; Tetramethoxysilane, tetraethoxysilane, tetra Tetraalfoxysilanes such as butoxysilane, trimethoxyneopentoxysilane, nomethoxynoneobentoxysilane; Alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; Noalkylnoalfoxysilane such as dimethylnomethoxysilane, trimethylnoethoxysilane; γ-chloropropyltrimethoxysilane, 3.3
．． 3-) Halogenated alkyl alkoxysilanes such as dichlorofurobyltrimethoxysilane; Alkylacyloxysilanes such as methyltriacetoxysilane and dimethyldiacetoxysilane; Hydrosilane compounds such as trimethoxysilane and triethoxysilane; Vinyltris) 4-disilane , vinylethoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane,
Monomers or polymers of unsaturated group-containing silane compounds such as γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, etc. , and further include their hydrolysates.

The hydrolyzate can be prepared, for example, in the presence of an acid or alkali catalyst,
It is synthesized by adding water to a silane compound having a hydrolyzable group in a combined alcohol system, and when an equivalent amount or more of water is added to the silane compound having a hydrolyzable group, it is completely hydrolyzed. An alcoholic silica gel, silica sol, or siloxane composite is obtained, and if less than an equivalent amount of water is added, a partial hydrolyzate corresponding to the ratio is prepared.

Among these silane compounds, especially the general formula (R' O)
3 S i [○S i(OR2)2] (OR')(
In the formula, R and R3 each represent the same or different alkyl group, aryl group, alkylaryl group, arylalkyl group, aryloxyalkyl group, or alkyloxyalkyl group, and 11 represents O or a positive integer. . ) Tetraalfukidisilane monomer or polymer shown by
Further preferred are compounds obtained by hydrolyzing a hydrolyzable group. Among these, compounds in which R' to R3 are each represented by the same or different alkyl groups having 4 or less carbon atoms are particularly preferred.

These silane compounds may be used alone or in combination of two or more.

The acrylic resin in the present invention refers to alkyl esters of acrylic acid or methacrylic acid (hereinafter referred to as (meth)acrylic acid alkyl esters) monomer alone or in combination with a flutenylbenzene monomer. It is obtained by polymerizing a mixture and a copolymerizable α,β-ethylenically unsaturated monomer according to conventional polymerization conditions.

Examples of the (meth)acrylic acid alkyl esters used in the present invention include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid [l-propyl ester, acrylic acid isopropyl ester, acrylic acid]
Lobethyl ester, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, 11-butyl methacrylate, 2-ethylhexyl methacrylate Examples include esters, decyl methacrylate, etc. Generally, the number of carbon atoms in the alkyl group is reduced to 1.
20 acrylic acid alkyl esters and/or methacrylic acid alkyl esters in which the alkyl group has 1 to 20 carbon atoms are used.

Examples of the alkenylbenzenes used in the present invention include styrene, α-methylstyrene, and vinyltoluene.

When using a monomer mixture of alkenylbenzenes and (meth)acrylic acid alkyl esters, it is usually ( The proportion of the meth)acrylic acid alkyl ester used is preferably 10% by weight or more.

Other copolymerizable α,β-ethylenically unsaturated monomers used to obtain the acrylic resin of the present invention include:
For example, α, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, 7-malic acid, crotonic acid, itaconic acid,
β-Ethylenically unsaturated carboxylic acids; α such as ethylene sulfonic acid.

β-ethylenically unsaturated sulfonic acids; 2-acrylamido-2-methylpropanoic acid: α,β-ethylenically unsaturated phosphonic acids; acrylonitriles; acrylamides; hydroxyl group-containing hydroxyalkyl esters of acrylic acid or methacrylic acid, etc. Vinyl monomers; amino esters of acrylic acid or methacrylic acid; glycytyl esters of acrylic acid or methacrylic acid; acrylic acid or methacrylates, and the like. These monomers may be used alone or in combination of two or more types of the acrylic resin of the present invention! i! Examples of the polymerization initiator used in the production include persulfates such as ammonium persulfate and potassium persulfate; organic peroxides such as acetyl peroxide and benzoyl peroxide. These are used in an amount of 0.1 to 10% by weight based on the total amount of monomers charged.

Acrylic resins can be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The obtained acrylic resin can be further added with a compound such as vinyl chloride/vinyl acetate resin, vinyl chloride resin, cellulose ether, etc.

The compound IC] is prepared by the following general formula [In the formula (I), R1 to R4 represent an alkyl group having 1 to 4 carbon atoms. ] A hinged amine compound containing one or more structural units represented by the following in one molecule is used.

Specific examples of hingoamine compounds containing one or more structural units represented by the above formula in one molecule include the following.

Guacetoxyyl, 2. A, A Tetramethylpiperidine (2) Voustearoyloxyl, 2. A, 6-methylpiperidinetetodacryloyloxyyl, 2. A, Otsu-Tetramethylpiperidine (phenylacetoquine), 2I2I Otsu, Ntetramethylbiverizin (phenoxyacetoquine) Uni, Otsu, A Chlorobenzoyloxy) Tetramethylbibenozine, 2I Otsu, A Tetramethylpiperidine (Hereafter, this will be referred to as C.Gunclohexanoyl oxane 22, Otsu, robenzyloxyx (1,, A, A Tetrantetramethylpiperidinylpiperidinegebenzoyl oxene/U2I Otsu, Otsutetra(1,0) (Phenylcarbamoyloxy)-, 2゜Methylpiperidine 2.6.A Tetramethylpiperidine αD G - Toluenesulfonyloxy) q-(2 Furoyloxy) U, Co, A, A -;, 21 O, 6 Tetramethylpiperidine Tetra Methylbiperidine (12+ glutoyloxy) co2, b 0!51 gβ naphthoyloxy) 2.2. A, A Tetramethylpiperidine Tetramethylpiperidine (+6) Bis(Co1.2.Otsu, Otsu-Tetramethyldavipe(+3) Innicotinoyloxy-2,2,1,,A Lysyl)oxanthotetramethylbis Veridine Wholesale Bisyu 1.2. Otsu, 6-tetramethylgebipebis 2,2, Otsu, Otetramethylgupiperidyl) malonate' Zil) fumaret I H Bisuyu, 2. /,,A Tetramethylguhype(2I) Bis,! , 2. Otsu, Otsu - Tetramethylpiperidyl)azibetridyl) Hexahydroterephtatobis(2,2, Otsu, Otsutetramethylbipezi2) Bis(,2,,2, Otsu, Otsutetramethylgebibenozyl) Sevagetridil) Terephthaleth (Hereinafter, this will be referred to as C 2-day trisuyu, yu, otto, ot-tetramethylgubiN5=c/N bejzyl) benzene/, :1,3 tricarboC=O xintotris2+, 2. Al1 Tetramethylgvidyl) Nitotriacetate (2(A) Tris2I2.A, 6 Tetramethylbiveridyl) Triazinyu, 4t, Otricarboxyzoltriacetate, U, Otsu, Otsu -tetramethyl-q Bitetrakis 2,2 , A.J.

Tetramethyluda Peridyl) Butane-1, Yu, 3 to Rikarboki piperi zil)butane l, yu, 31φ Tetra Nle to Calfoxyle to (below, This is C ) Te trachis 2, ;l, Otsu, Otsu Tetramethyl Game piperidyl) centre Rohan / , / , 2, J Te to La Carbo Kisole to to squirrel Yu, 2. M-M Tetramethyl derby Veridil) Yu Acetoxypropane-/.

3 Tricarboxyleto○0CCH3 -32= Tris(2,a,t,,,A-tetramethyl-9-bi,
umbellidyl)-euhydroxyfluoroha f -1°, 2.3 Tricarboxylate H Trisco, 2. b, A tetramethyl-derpiperidine) phosphite a/, 3. g Triaza 7.7, 9.9 Tetramethylrouyl, Dashioxospiro [q, s ] Deca n = q ~ Oton average molecular weight - approximately 3,000 0 = C NI ( (Chisamo Chimica Ogani Chikara Nis Bi Ni Co., Ltd.) (manufactured by CHIMAS BORB 911 da) tri(q-acetoxy-2,2I, 6-titramethylpiperidine)-amine n-glue average molecular weight - approx. 3,000 (manufactured by Ciba Geigy Co., Ltd. Tinuvin A+22) (manufactured by Ciba Geigy Co., Ltd. Tinuvin / Guda) Tetraquinu (2,,2,Otsu,Otsu-tetramethyl-dapiperidyl)propane-7,/,J,,3-tetracarboxylate P,H or/,3.g-)Riaza,ri,7,9.9- Tetramethyl-3-n-octyl-spiroCq,s]]decanoyl, ψ-dione38) (,2,,2,Otsu,Otsu-tetramethylpiperidine)Goosespiro-λ'-(Otsu',6'-dimethyl Hyhelidine)
a'-spiro-5'L Hindantoin 0 = O-NH = 36- (43/, 3.g -) Reazor 7. 9,9-tetramethyl 2% I-dioxose spiroCp,s:]decane0=C-NH The blending ratio of the silane compound [A] and the acrylic resin [Bl is [AI to [Bl] is 20% by weight. 1 to 15 to 1 to 15
It is preferable that it is within the range of . If the proportion of the silane compound [A] exceeds the above range, the coating formed on the molded product will become brittle, have poor adhesion to the base material, and will easily peel off, which is undesirable. If the proportion of Bl is above the above range, the effect of stain resistance will not be significantly exhibited, which is not preferable. Among the above ranges, it is particularly preferable that [A] to [Bl be in the range of 15:1 to 1:10.

In addition, the preferable amount of the hinged amine compound [C] used in combination with the coating is the weight ratio of the silane compound [A] to the total organic component of the -Sho acrylic resin [B].
] + [B] vs. [C] is 100:0.1 or 100:5
The range is 0. If the proportion of the hindered amine compound is below the above range, it has little effect on the water resistance and clay song resistance of the coating, and is therefore undesirable. Even if it is added in excess of the above range, the performance improvement effect proportional to the amount added cannot be obtained, and the transparency of the film is impaired, which is not preferable. Among the above ranges, especially [A] + [B] vs. [C] is 1
Preferably, the range is from 0.00 to 0.5 to 100.30.

A liquid dispersion medium may be further added to the above composition as required. Examples of liquid dispersion media include 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 dibenzyl alcohol; and cellosolve acetates. ; Examples include ketones, acetate esters, aliphatic hydrocarbons, and aromatic hydrocarbons.

These liquid dispersion media may be used alone or in combination, but
It is preferable to decide by taking into consideration the dispersion stability of the coating composition, the wettability to the surface of the molded article when a coating method is used, the difficulty of removing the liquid dispersion medium, and economic efficiency.

The above coating composition may further contain small amounts of acid to alkali 17m foaming agents, surfactants, lubricants, antistatic agents,
Antioxidants, ultraviolet absorbers, film forming aids, thickeners, pigments,
Conventional additives such as pigment dispersants, fungicides, algaecides, and inorganic fillers can be mixed.

When applying the above-mentioned coating composition to the surface of the synthetic resin base material, any method known per se such as roll coating method, dip coating method, spacing coating method, spray coating method, bar code method, knife coating method, etc. may be used. good.

When the coating composition is formed as a single film without being in a solution state, a coextrusion method, an extrusion coating method, an extrusion lamination method, and a lamination method are used.

A coating coated with the coating composition described above is formed on the surface of an agricultural vinyl chloride resin film under heat treatment. This results in a silane compound, acrylic i? , m fat and hindered amine compounds chemically combine to form a strong film with excellent barrier properties against contaminants, resulting in improved stain resistance.

Examples of heat treatment methods when using a coating method as a coating method include hot air heating, infrared heating, and far infrared heating.However, in consideration of heat treatment efficiency and safety, hot air heating is is advantageous.

In this case, the temperature conditions should be in the range of 50 to 200°C, and the time should be selected between 10 seconds and 60 minutes.

Agricultural vinyl chloride-based O (the amount of solid matter adhered to the film formed on the surface of the fat film under heat treatment is preferably 0)
．． It is suitable that it is in the range of 1 to IOg/m2. 0
, 1 g/In2, the effect of preventing the plasticizer from migrating to the surface of the soft vinyl chloride resin film is insufficient. Moreover, if it is 10 g7162 or more, the amount of coating is too large, which may be economically disadvantageous, and the mechanical strength of the film itself may decrease. Therefore, usually
The most preferred range is 0.5 H/+n2 to 7 g/m2.

In addition, before coating with the above-mentioned coating composition, the surface of the soft vinyl chloride resin film is washed with alcohol or water, subjected to plasma discharge treatment or corona discharge treatment, or undercoated with other paint or primer. Pretreatment such as the following may be performed.

When the agricultural vinyl chloride resin film according to the present invention is actually used for agricultural purposes, when the coating is formed on only one side, the side on which this coating is provided will be the outside of the greenhouse or tunnel. Use it as follows.

"Function" The agricultural vinyl chloride resin film according to the present invention has a coating coated with a specific coating composition formed on its surface, and this coating prevents oozing of various resin additives blended into the film. Even if the film is stretched outdoors for a long time, there will be little surface contamination and little decrease in light transmittance. Furthermore, by incorporating the hinged amine compound, this coating has excellent flexibility, water resistance, and crazing resistance.

Moreover, since the base film contains a fi +7 phosphate ester and/or an organic phosphate metal salt, the elongation retention rate is high and the durability is also excellent.

“Examples” The present invention will be explained in detail based on Examples below.
The present invention is not limited to the following examples unless they exceed the scope of the invention.

To Examples 1 to 6 and Comparative Example 1 75 Preparation of base film Polyvinyl chloride (P=1400) 100 parts by weight Dioctyl 7-talate 50 Epicor) 82
8 (Epoxy compound, trade name manufactured by Shell, USA) 1〃Ba/Zn
Composite stabilizer 1.5 Barium stearate (stabilizer) 0.2 Zinc stearate
0.4 Sorbitan monolaurate 1.5
A resin composition consisting of 0.2% of a benzo-7ene-based ultraviolet absorber was prepared, and organic phosphate esters and/or organic phosphate metal salts of types and amounts shown in Table 2 were blended. However, in Comparative Examples (1, 2), it was not blended.

Each formulation was stirred and mixed using a super mixer for 10 minutes, and then kneaded on a mill roll heated to 180°C to prepare a base film having a thickness of 0.15+n+n.

Acrylic, lunar production Examples 1 and 4 Into a reactor equipped with a thermometer, stirrer, reflux condenser, and nozzle for adding raw materials, add 100 parts by weight of isopropyl alcohol, 1.0 parts by weight of benzoyl peroxide, and Table 1. Add 100 parts by weight of the mixture of each monomer shown in , stir at 80°C for 3 hours in a nitrogen gas stream, and then add 0.5 parts by weight of benzoyl peroxide and continue the reaction at the same temperature for about 3 hours. Then, acrylic resin A-''D was obtained.

A coating composition was prepared by blending a silane compound, an acrylic resin, and a hinged amine compound in the types and amounts shown in Table 2 and adding isopropyl alcohol so that the solid content was 20% by weight. I got something.

However, in Comparative Example 1, no silane compound was blended. Furthermore, in Comparative Example 2, no acrylic resin was blended.

Each of the above coating compositions was applied to one side of the base film prepared by the above method using a #5 percoater.

The coated film was held in an oven at 130°C for 3 minutes to volatilize the solvent and at the same time heat-treated.

However, in Comparative Example 6, after applying the coating composition, the solvent was volatilized by natural drying without heat treatment. The amount of coating on each film obtained was approximately 2 g/+n2.

Film Evaluation The performance of the film was evaluated in the following manner and the results are shown in Table 2.

(2) Flexibility of the coating Each film was cut into pieces with a width of 5c+n and a length of 15cm, which were folded back alternately at 2cm intervals in a direction perpendicular to the length direction. In this state, apply a load of 2 kg from above, and
It was left in a constant temperature bath kept at 5°C for 24 hours. Then, the load was removed, the folds of the film were stretched out, and the appearance of the film was observed with the naked eye.

The results are shown in Table 2. The evaluation criteria for this test are as follows.

◎...No change is observed in the film at the crease.

△...Cracks are observed in the coating at the creases.

×: Cracks are observed in the coating at the creases.

■ Outdoor expansion test 11 types of films were installed in a roof-type greenhouse (width: 3+++, depth: 5 mm, Mukudori: 1 mm) in a test field in Shigun, Mie Prefecture.
, 5 m, roof slope 30 degrees) with the coated side facing outside the house, and from April 1985 to 1988
A two-year extended examination was conducted until March 2017.

The stretched film was subjected to an external appearance test and the elongation retention rate of the film was measured by the following method, and the dust resistance of the film during the stretching test was evaluated.

Appearance of film: Appearance observed with the naked eye.

The evaluation criteria are as follows.

◎...No change in appearance such as discoloration is observed.

○: Some changes in appearance such as slight discoloration are observed.

△: Appearance changes such as discoloration are observed.

×: Discoloration is observed on the entire surface.

Elongation retention rate of film...means a value calculated by the following formula.

The measurement results were displayed as follows.

◎...Light transmission after expansion f! 4 rate is 90% or more of before expansion.

○...The light transmittance after stretching is in the range of 70 to 89% of that before stretching.

Δ...The light transmittance after expansion is in the range of 50 to 69% of that before expansion.

×: The light transmittance after stretching is less than 50% of that before stretching.

Dustproof property: means a value calculated using the following formula.

Direct light transmittance at a tree wavelength of 555 mμ (newly manufactured by Hitachi, EPS-2U type used) ``Effects of the Invention'' As is clear from the examples above, the present invention has the following effects, which improves agricultural performance. The above utility value is extremely large.

(1) Even when the agricultural vinyl chloride resin film according to the present invention is stretched outdoors for a long period of time, there is little discoloration, deterioration in physical properties, or deterioration in dust resistance, and it can be used for a long period of time.

(2) The agricultural vinyl chloride resin film according to the present invention has a coating formed on the surface of the base film that has excellent adhesion to the base film and is highly flexible.
The coating is difficult to peel off and can withstand long-term use.

Patent applicant: Mitsubishi Kasei Vinyl Co., Ltd.

Claims (3)

[Claims] (1) A silane compound [A] having a hydrolyzable group directly bonded to a silicon atom and acrylic acid or A monomer selected from alkyl esters of methacrylic acid (hereinafter referred to as (meth)acrylic acid alkyl esters), or a mixture of this and an alkenylbenzene monomer, and copolymerizable α, β - Agricultural vinyl chloride produced by heat-treating a coating mainly composed of an acrylic resin [B] obtained by polymerizing an ethylenically unsaturated monomer and a hindered amine compound [C]. system resin film. (2) The silane compound [A] has the general formula (R^1O)_3
Si[OSi(OR^2)_2]_n(OR^3)_n
(In the formula, R^1 to R^3 each represent the same or different alkyl group, aryl group, alkylaryl group, arylalkyl group, aryloxyalkyl group, or alkyloxyalkyl group, and n is 0 or Agricultural vinyl chloride according to claim 1, which is a compound obtained by hydrolyzing a tetraalkoxysilane monomer or polymer represented by (representing a positive integer) or a hydrolyzable group. system resin film. (3) The hindered amine compound [C] has the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ...... (I) [In the formula (I), R^1 to R^4 have 1 to 1 carbon atoms. 4 shows the alkyl group. ] The agricultural vinyl chloride resin film according to claim 1 or 2, which is a hindered amine compound containing one or more structural units represented by the following in one molecule.