JPH03231848A - Agricultural polyvinyl chloride-based resin film - Google Patents

Abstract

PURPOSE:To prevent the transparency of the film concerned from lowering due to the development of algae by a method wherein coat, the major components of which consist of three components or silane compound, acrylic resin and organic nitrogen-based algaeproofing agent, is produced on flexible polyvinyl chloride-based resin film by heating. CONSTITUTION:Three components or silane compound (A), which has hydrolyzable group directly bonded to silicon atom, acrylic resin (B), which is synthesized by polymerizing alkyl esters of acrylic acid or of methacrylic acid or their mixture with alkenylbenzenes and copolymerizable alpha,beta-ethylenically unsaturated monomers, and organic nitrogen-based algaeproofing agent (C) are blended together and dispersed in liquid dispersing medium such as alcohols or the like so as to prepare coating liquid. By applying said coating liquid on one side or on both sides of flexible polyvinyl chloride-based resin film and, after that, drying, above-mentioned three component coat is produced so as to obtain agricultural polyvinyl chloride-based resin film.

Description

Detailed Description of the Invention "Industrial Application Field 1 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 a decrease in transparency caused by the growth of algae when spread outdoors. Vinyl chloride J [Related to fat film.

[Conventional technology J] In recent years, with the expansion of greenhouse horticulture, the facility area has increased, and agricultural vinyl chloride PS! ! II fat film is increasingly being used in various regions. As the environments in which they are used have become more diverse, the environmental conditions inside and outside the greenhouses have become relatively hot and humid. In addition to blocking the transmission of light, there are also many cases where the mechanical strength of the film is reduced.

In general, algae are microorganisms that exist in surface water, and because they contain chlorophyll, they have the ability to photosynthesize, and the surface is often covered with a sticky substance, so the growth of algae on film can be prevented by physical or mechanical methods. It is difficult to defend +L or remove the ones that occur.

To remove algae from conventional algae-infested films,
The only options are to physically scrape it off or let it dry and wait for it to fall off naturally, but either method is difficult to do in large facility houses. It is possible to kill type I by using chemicals such as sodium hypochlorite aqueous solution to thin the film, but it is necessary to remove dead algae from Film-L, and the film thinning effect is reduced. cannot be expected to last long.

[Problem to be Solved by the Invention 1] Under such circumstances, the present inventors have devised a method to prevent the decrease in transparency accompanying the growth of algae caused by spreading outdoors.
The present invention has been completed as a result of intensive studies aimed at providing an agricultural vinyl chloride resin film that has an excellent long-lasting algae-proofing effect. [Means for Solving the Problems] Therefore, the gist of the present invention is that a silane compound [Al, a specific acrylic resin [B] and an organic The present invention relates to an agricultural vinyl chloride-based n4N film formed by heat treatment to form a film of a composition containing three components as main components: nitrogen-based algae-proofing EC].

The present invention will be explained in detail below.

In the present invention, the vinyl chloride resin refers to polyvinyl chloride as well as a copolymer whose main component is vinyl chloride.

Examples of monomer compounds copolymerizable with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, maleic acid, itaconic acid, acrylic acid, methacrylic acid, vinyl acetate, and the like. 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.

In order to impart flexibility to the vinyl chloride resin that serves as the substrate described in , 20 to 60
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, heptatalic acid derivatives such as no-n-octyl 7-talate, no-2-ethylhexyl 7-talate, nobenzyl 7-talate, nododecyl 7-thale, nododecyl 7-thale, nododecyl 7-thale; etc. in7talic acid derivative; No 11-
7 divic acid derivatives such as butyl anovate, no-octyl anovate; maleic acid i such as no-11-butyl maleate
4 bodies; citric Wl derivatives such as F-lylopyl citrate; itaconic acid derivatives such as mo/butyl itaconate;
Oleic acid derivatives such as butyl oleate F; Lysyl/lysyl acid derivatives such as glycerin mo/lysyl phosphate; Other organic phosphoric acid esters such as tricresyl phosphate and tricylenyl phosphate, epoxidized soybean oil, and epoxy resin I
Il? Examples include plasticizers.

In addition to the plasticizer, the vinyl chloride resin may also contain, if necessary, known resin additives that are usually added to synthetic resins for molding, such as lubricants, heat stabilizers, ultraviolet absorbers, Antioxidants, stabilizing agents, antistatic agents, anticorrosive agents, non-W1 fillers, colorants, etc. can be blended.

Examples of lubricants, heat stabilizers, or antioxidants that can be blended into the film of the present invention include polyethylene wax, bisamide compounds, rough-in, organic 7-osphite compounds, β-noke 7 compounds 4&I, Examples include piperinone-based hinged amine compounds.

Each of the PA resin additives listed in 1- above can be used as IM or in combination.

The amount of the various resin additives mentioned above can be selected within a range that does not deteriorate the properties of the film, usually within a range of 10 parts by weight or less based on 100 parts by weight of the base vinyl chloride resin.

To blend the plasticizer and other resin additives into the vinyl chloride resin that serves as the base of the film, weigh the necessary amounts of each and use a conventionally known method such as a ribbon blender, Banbury mixer, super mixer, etc. A blender or mixer 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-
For example, the method may be a method such as the Gouy method, the In7reshi3in method), the calender molding method, or the solution casting method.

The agricultural vinyl chloride fruit tree WI film of the present invention has a coating mainly composed of a silane compound, a specific acrylic fruit resin, and an organic nitrogen-based algae-proofing material formed on one or both sides of the film by heat treatment. ing.

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

Specifically, aminomethyltriethoxysilane, N-β
-aminoethylaminomethyltrimethoxysilane, γ-
Aminopropyltrimethoxysilane, N-()rimethoxysilylbuvir)-ethylenenoamine, N-(dimeF
7 such as ethylenenoamine, etc.
Mi/alkylflucoquine silane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethylno/Foxysilane, β-(3,4-dipoquinecyclohexyl)ethyltrimethoxysilane, β-( 3,4
-Epoxyalfluorucoxysilanes such as ethylmethylnomethoxysilane; -Flucaptoalkylfurkoxysilanes such as γ-mercaptopropyltrimethoxysilane and γ-flucaptopropylmethyldimethoxysilane: tetramethoxysilane, tetramethoxysilane, etc. Tetraalkoxysilanes such as ethoxysilane, tetrabutoxysilane, trimethoxyneopentoxysilane, and dimethoxynoneobentoxysilane; Furkyltoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane Flukoxysilane; Dialkyldialkoxysilane such as nomethylnomethoxysilane and dimethylnoethoxysilane: γ-chloropropyltrimethoxysilane, 3.3
．． 3-) Halogenated alkyl alkyloxysilanes such as dichloropropyltrimethoxysilane; Furkylacyloxysilanes such as methyltriacetkinsilane and methyldiacetoxysilane; Hydrosilane compounds such as trimethoxysilane and triethoxysilane; Vinyl Trimethoxysilane, vinylethoxysilane, vinyltris (β-
methoxyethoxy) silane, arifletriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)7cryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, etc. Examples include monomers or polymers of saturated group-containing silane compounds, as well as hydrolysates thereof.

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 sol or silica sol/siloxane-based 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'0)ss
i[O8i<0R2)2]<OR') (where R~R
3 are the same or different alkyl groups, aryl groups,
represents an alkyl 7-aryl group, an arylfurkyl group, a 7-ary axyalkyl group, or an alkyloxyalkyl group,
The monomer of tetraalfoxydisilane represented by (n represents O or a positive integer) is preferably a polymer, and more preferably a compound obtained by hydrolyzing a hydrolyzable group. In particular, R' and R2 each have the same or different number of carbon atoms 4
Compounds represented by the following alkyl groups are preferred.

These silane compounds may be used alone or in combination in amounts of 2M or more.

In the present invention, the acrylic #4II'ff refers to a monomer of acrylic acid alkyl esters alone, a crushed product of this monomer and an alkenylbenzene monomer, and copolymerizable a, β - an ethylenically unsaturated monomer under conventional polymerization conditions.

The (meth)acrylic acid furkyl esters used in the present invention include, for example, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid-lowpropyl ester, acrylic acid isopropyl ester, acrylic acid-
n-butyl ester, acrylic acid-2-ethylhexyl ester, acrylic acid decyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, / tacrylic acid-n
-propyl ester, isopropyl methacrylate, 〇-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, etc. Generally, the number of carbon atoms in the furkyl group is 1-
, 20 acrylic acid alkyl esters and/or 7-tacrylic acid alkyl esters in which the alkyl group has 1'...20 carbon atoms are used.

As alkenylbenzenes used in the present invention: 1. t
Examples of 1M 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 acrylic acid alkyl ester used is preferably 10% by weight or more.

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

β-ethylenically unsaturated sulfonic acids; 2-acrylami)'-2-methylpropanoic acid; a,β-ethylenically unsaturated phosphonic acids; acrylonitriles; acrylamides: acrylic acid or methacrylic acid amide 7
Esters; glycytyl esters of acrylic acid or methacrylic acid; acrylic acid or 7-tacrylates, and the like. These monomers may be used alone or in combination of two or more.

Examples of the polymerization initiator used in producing the acrylic resin of the present invention include persulfates such as ammonium persulfate and potassium persulfate; organic peroxides such as acetyl peroxide and benzoyl peroxide.

These are 0.1 to 10% of the total amount of monomers incorporated.
Used within a range of %.

Acrylic resins can be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The obtained acrylic resin is further used by adding a compound such as vinyl chloride/vinyl acetate 01 resin, vinyl chloride resin, cellulose ether, etc.

The organic nitrogen-based algaecide used in the present invention [C1 is a silane compound [a compound that chemically bonds with or has affinity with a hydrolyzable group such as a silyl group or an alkoxy group in Al] For example, 2-(4-thiazolyl)
-Benzimiguzole, 2-methoxycarbonylamide/
- Imigusol derivatives such as benzimigusol; 3
, 4.5-) 7nilide derivatives such as lipromsalicylanilide; urea derivatives such as 3-toJfluoromethyl-4,4'-dichloro-N, N'-nochloro-N, N'-biphenylurea; N- Methylnotiocarbamine W & ammonium derivatives such as tetradecyldimethylpencylammonium chloride; 2.3.5
.

Pyridine derivatives such as 6-tetrachloro4(methylsulfonyl)pyridine; 2-7tilthio4-terL-
Tri7one derivatives such as butylamino/-6-cyclopropyl-amino-S-trianone; N.

N-tumethyl-N'-(fluoronochloromethylthio)
-N-/NG alkylthio derivatives such as -N'-phenylsulfamide: N-(fluoronochloromethylthio)-7talimide, N-1,1,2,2-tetrachloroethylthiotetrahydro7talimide, etc. 7-talimide derivative: 2,4.5.6-titrachloroiso7
Nitrile derivatives such as thalonitrile; benzothiazole derivatives such as 2-(4-thiocyanomethylthio)benzothiazole; 4-1j methylsilylbennor7mine and the like;
1! ! Bennolamine derivatives; examples include dithiocarbamate derivatives such as tetramethylthiuram disulfide. These organic nitrogen-based algae-preventing agents may be used alone or in combination of two or more, and if necessary, other organic nitrogen-based algae-preventing agents such as parachloromethaxylene may be used. It is okay to use algae agents at the same time.

The blending ratio of the silane compound [A] and the acrylic resin [13] is preferably such that [A]N[B] is in a weight ratio of 20:1 to 1:15. If the ratio is in the above range or more, t is formed on the film.
This film becomes brittle, has poor adhesion to the base material, and is easily peeled off. Furthermore, if the proportion of the acrylic 01 fat [B] is less than the range 1-, the anti-algae effect becomes extremely difficult to exhibit. Therefore, in particular, [A1 vs. [B
1 is preferably in the range of 15:1 to 1:10.

The amount of organic nitrogen-based algae-proofing [C1] is the silane compound [A
1 to 1 to rcIAr in weight ratio per formed component
Preferably, the range is from 1 to 100 to 70. When the ratio of organic nitrogen-based algae-proofing [C1] is less than the range 1-, the transparency of the film formed on the film decreases, and the adhesion to the base material is poor, making it easy to peel off. . Furthermore, if the proportion of the organic nitrogen-based algae-preventing material [C1] is below the above range, it will be difficult to exhibit a sufficient algae-preventing effect. Among these, it is particularly preferable that [A1 to rc1 is in the range of 100 to 5 to 100 to 50.

A liquid dispersion medium may be further added to the above composition as required. As the liquid dispersion medium to be used, methyl alcohol,
Monohydric alcohols such as ethyl alcohol and isopropyl alcohol; Polyhydric alcohols such as ethylene glycol, noethylene glycol, and glycerin; Cyclic alcohols such as dibennor alcohol; Cellosolve acetates; Acetate esters; Aliphatic hydrocarbons aromatic hydrocarbons; alicyclic hydrocarbons; ketones, etc.

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 after coating on the film surface, the difficulty of removing the liquid dispersion medium, and economic efficiency.

-1- In addition, a small amount of acid or alkali, antifoaming agent, surfactant, lubricant, antistatic agent, plasticizer, antioxidant, crosslinking agent, ultraviolet absorber, light stabilizer,
Conventional additives such as a film-forming agent, binder, pigment, pigment dispersant, and inorganic filler can be mixed.

Various known methods can be applied to apply the coating composition to form a coating on the surface of the soft vinyl chloride resin film. For example, when forming a film in a solution state, the doctor blade foot method, gravure roll coating method, air knife coating method, reverse roll foot method, dip foot method, brush coating method, spray coating method, bar code method, etc.
Any method known per se such as a knife coating method may be used.

When the coating composition described in t 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 film derived from the above coating composition is formed on the surface of a soft vinyl chloride resin film under heat treatment. The heat treatment chemically bonds the silane compound and the acrylic resin, resulting in a strong film with excellent barrier properties against pollutants, which suppresses the attachment and growth of algae. Furthermore, heat treatment creates a chemical bond between the silane compound and the organic nitrogen-based algae preventive coating, or the affinity between the two is strengthened, so there is no risk that the organic nitrogen-based algae preventive coating will be leached from the coating surface. The anti-algae effect lasts for a long time. Heat treatment methods when using a coating method as a coating method include, for example, hot air heating, infrared heating, far infrared heating, etc. However, in consideration of heat treatment efficiency and safety, hot air heating is right-handed. In this case, the temperature conditions are 50.IX, 200℃, and the time is 10 seconds.
It is best to choose the opening of a O minutes.

The amount of the coating formed on the surface of the soft vinyl chloride resin film by heat treatment is preferably in the range of 0.1^.10 g/2. If it is less than 0.1 g/-2, the effect of preventing the plasticizer from migrating to the surface of the soft vinyl chloride resin film is insufficient. Moreover, if it is 10g7m2 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, the range of 0.5 to 7 g/m2 is usually most preferred.

In addition, before coating with the coating composition mentioned above, the surface of the soft vinyl chloride TJ (oil film) should be cleaned with alcohol or water, plasma discharge treatment, corona discharge treatment, or treated with other paints or primers. Pretreatment such as undercoating 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 should be the outside of the greenhouse or tunnel. and use it.

Hereinafter, the present invention will be explained in detail based on examples.
The present invention is not limited to the following examples unless they exceed the scope of the invention.

Example 1-=, 5, Comparative Example 1 26 Polyvinyl chloride (P=14001 100% octyl 7-talate 50 Triphrenol phosphate 5 Ebifuto 828 (epoxy compound, USA) (Product name manufactured by Shell) 1Ba/Zn composite stabilizer 1.5 Barium stearate (stabilizer) 0.2/Zinc stearate
0.4 〃Nrubitanmo/laurate
1.5 〃2.4-Dihydroxybenzo7ene 0.
A resin composition consisting of 3 was prepared, mixed with a super mixer with partial stirring using a super mixer, and then kneaded on a mill roll heated to 180°C to prepare a base film having a thickness of 0.15 mm.

Ahri! --100wt of isopropyl alcohol in a reactor equipped with a thermometer, a stirrer, a reflux condenser, and a nozzle for adding raw materials.
1.0 parts by weight of benzoyl peroxide and 100 parts by weight of a mixture of each monomer shown in Table 1 were charged, and benzoyl peroxide was further heated at 80° C. for 3 hours while stirring in a nitrogen atmosphere. 0.5 parts by weight of was added and the reaction was continued at the same temperature for about 3 hours to obtain 7D in acrylic resin A.

Formation of 1 film: A silane compound of the type and amount shown in Table 2, an acrylic resin, and an organic nitrogen-based algae-proofing material are mixed, and isopropyl alcohol is added to the mixture so that the solid content is 20% by weight. A composition was obtained.

The coating composition described above was applied to one side of each of the base films prepared by the above method using a #5 bar coater. The coated film was kept in an oven at 130°C for 3 days to volatilize the solvent and at the same time heat treatment was performed. 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/m2.

Evaluation of Film 4 The performance of the film was evaluated in the following manner and the results are shown in Table 3.

(2) Flexibility of Coating Each film was cut into pieces of 5 cm wide and 15 cm long, and folded back alternately at intervals of 2 cm in a direction perpendicular to the length. In this state, apply a load of 2 kg to the
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 3. 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.

×: Significant cracks are observed in the film at the creases.

■ Outdoor expansion test 11 types of films were tested in a roof-type house (frontage 31-1 depth 5 wheels, ridge height 1
．． 5+*, roof slope 30 degrees), the coated surface was coated on the outside of the house from May 1986 to April 1999.
Expansion tests were conducted for two years until March.

The stretched film was periodically evaluated for algae-proofing properties and dust-proofing properties by the following methods.6 The results are shown in Table 3.

Algae resistance: Visual observation of algae growth.

The evaluation criteria are as follows.

◎...No algae growth observed on the surface.

○: Slight algae growth is observed on the surface.

Δ...The surface is covered with algae growth.

×: Algae has grown and grown over the entire surface.

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

Direct light transmittance at Hondo length 555-μ (manufactured by Hitachi, EPS-2U model used) Measurement results were displayed as follows.

◎...Light transmittance after stretching is 90% or more of that before stretching 6 0... Light transmittance after stretching is 70'89% of that before stretching
Those in the range of.

△...Light transmittance after expansion is 50'\69 before expansion
% range.

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

Table 3: Effects of the Invention 1 The present invention has the following effects, and its utility value in agriculture is extremely large.

(1) Even when the agricultural vinyl chloride resin film according to the present invention is extended outdoors for a long period of time, the degree of deterioration in algae-proofing property and dust-proofing property is small and it can withstand long-term use.

(2) The agricultural vinyl chloride PS 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 transparent.
The coating does not easily peel off and can withstand long-term use.

Claims (1)

[Claims] (1) A monomer selected from a silane compound [A] having a hydrolyzable group directly bonded to a silicon atom and an alkyl ester of acrylic acid or methacrylic acid, or the like, on one or both sides of the soft vinyl chloride resin film. and alkenylbenzene monomers, and copolymerizable a, β
- A film of a composition whose main components are an acrylic resin [B] obtained by polymerizing an ethylenically unsaturated monomer and an organic nitrogen-based algae-proofing material [C] is formed under heat treatment. This is an agricultural vinyl chloride resin film.