JPS62283135A - Vinyl chloride resin film for agriculture - Google Patents

Abstract

PURPOSE:The titled film keeping improved water resistance and anti-fogging properties for a long period, obtained by coating one side of both sides of a specific non-rigid vinyl chloride resin film with an anti-fogging agent containing aqueous emulsion of a specific hydrophobic acrylic resin, etc. CONSTITUTION:One side or both sides of a non-rigid vinyl chloride resin containing an ultraviolet light absorber and an organic phosphoric acid ester are coated with an anti-fogging composition comprising both (A) aqueous emulsion of hydrophobic acrylic resin having 35-80 deg.C glass transition temperature obtained by subjecting A1: 60-100wt% monomer consisting of a (meth)acrylic acid alkyl ester (e.g. methyl acrylate, etc.) or monomer mixture of the (meth) acrylic acid alkyl ester and an alkenylbenzene (e.g. styrene, etc.) and A2: 0-40wt% another alpha,beta-ethylenic unsaturated monomer (e.g. acrylic acid, etc.) copolymerizable with the component A1 to emulsion polymerization and (B) inorganic colloidal sol, etc.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Application of R Projection) The present invention relates to an agricultural soft vinyl chloride resin film, more specifically, an agricultural soft vinyl chloride resin film with improved antifogging properties. The present invention relates to vinyl-based tree films.

(Prior art and its problems, α) Nowadays, farmers who cultivate useful plants are widely using methods of accelerated cultivation or stamp cultivation of useful plants in greenhouses or tunnels for the purpose of increasing profitability. started to be adopted.

For this agricultural house or tunnel W1'R village, polyethylene film, ethylene-vinyl acetate Jt+
29. o Body film, polyester film, polycarbonate film, vinyl chloride film (fat film, glass, etc.) are used.Among them, vinyl chloride film (fat film, especially soft vinyl chloride resin film containing a large amount of plasticizer) are used. is widely used because it has the best overall light transmittance, heat retention, mechanical strength, durability, workability, economic efficiency, etc. compared to other synthetic resin films, glasses, etc. ing.

However, when a soft vinyl chloride fruit tree 11'l film is used to cover a greenhouse or tunnel, the penetration of sunlight becomes poor due to the cloudy interior of the greenhouse, slowing down plant growth, and causing water droplets to damage the cultivated plants. If the seeds fall, young shoots may be damaged or cause diseases.

In order to eliminate such inconveniences, it is known that antifogging properties may be imparted to the surface of the soft vinyl chloride resin film. In order to impart antifogging properties to the surface of a soft vinyl chloride resin film, there is a method of kneading a hydrophilic substance such as a surfactant into a soft vinyl chloride resin film and forming it into a film. A method of coating the surface with a water-soluble polymer substance, which is likely a hydrophilic substance, is being explored.

However, in the former method, the hydrophilic substance kneaded into the soft vinyl chloride resin oozes out onto the film surface.
Coordination gives the film antifogging properties, but it is easily washed away by water (a As time passes, the antifogging properties decrease.To solve this problem, for example, Japanese Patent Publication No. 46-13
No. 252, JP-A No. 49-70885, and JP-A-50-71770 describe a method of applying a water-soluble hydrophilic substance such as polyvinyl alcohol, and a method of applying a water-soluble hydrophilic substance such as polyvinyl alcohol.
No. 0-6437 and Japanese Patent Publication No. 53-37075 propose a method of applying a composition comprising a hydrophilic polymer containing hydroxyalkyl acrylate as a main component, a surfactant, etc. However, these hydrophilic substances are susceptible to hydrolysis and therefore have poor water resistance, and also have poor adhesion to hydrophobic soft vinyl chloride resins. Particularly under humid conditions, coatings derived from these hydrophilic substances
In order to improve these drawbacks, such as the fact that the resin film easily peels off from the surface and cannot exhibit sufficient antifogging performance, for example,
No. 219 proposes a method of making a hydrophilic acrylic acid ester Mffi compound containing a hydroxyl group insoluble in water using a crosslinking agent. However, according to this method, the antifogging property itself also decreases, so it cannot be said to be a satisfactory improvement method.

On the other hand, as a substance that imparts hydrophilicity, No. 8! For example, in Japanese Patent Publication No. 11348/1983, a method of applying a mixture of aqueous sol and surfactant is proposed.
Japanese Patent Publication No. 49-326G8 describes a product in which a surfactant is added to alumina sol, and JP-A-58-29831 describes a product in which a small amount of water-soluble aluminum salt is added to colloidal silica. There is. However, there are 8 mixtures of these! What is the quality of soft vinyl chloride resin? Due to the poor FF adhesion, the formed coating film falls off over time, making it impossible to maintain the desired anti-fogging effect on the hair.

In order to improve the above drawbacks, for example, Japanese Patent Application Laid-Open No. 51-818
No. 77 discloses an alumina sol containing a surfactant and a hydrophilic polymer, JP-A-57-119974, JP-A-57-187347, vfWR 1987-
15473 'l Public 11 +: C. A product in which a hydrophilic polymer and a surfactant are added to colloidal silica is disclosed. However, these compositions contain no 8! Since hydrophilic polymers such as polyvinyl alcohol and hydroxyl group-containing acrylic L4 resin are blended for the purpose of achieving miscibility with aqueous sol, the formed coating film tends to be inherently inferior in water resistance. Therefore, if you are constantly exposed to humid conditions, there will be no 8! The aqueous sol is washed away with the hydrophilic polymer, causing poor dispersion, and the antifogging effect is lost in a short period of time.
This is not actually satisfactory.

Furthermore, in order to improve the above deficiency and α, for example,
99976 and JP-A-55-99987 propose a method of imparting antifogging properties using a Kuroiso-organic composite reaction product consisting of silica/hydrophilic polymer/organosilicon compound. However, even with these methods, the water resistance of the formed coating film is not sufficient, and the antifogging performance is not yet satisfactory, so that it is difficult to fully achieve the intended purpose.

(Means for Solving the Problems) The present inventors solved the above-mentioned conventional drawbacks and provided a soft vinyl chloride-based 8 (N film) that exhibits excellent water resistance and antifogging properties over a long period of time. As a result of intensive study, we have completed the present invention.

That is, the gist of the present invention is that (a) 60 to 100% by weight of a fullyl ester of acrylic acid or methacrylic acid is applied to one or both sides of a soft vinyl chloride resin film that absorbs ultraviolet light and contains an organic phosphate ester. a monomer or a mixed electrolyte of an alkyl ester of acrylic acid or methacrylic acid and an alkenylbenzene, and an α,β-ethylenic material thereof that can be copolymerized with 0 to 40% by weight of the above-mentioned insect polymer. Hydrophobic acrylic PS with a glass transition temperature in the range of 35 to 80°C, obtained by emulsion polymerization with an unsaturated monomer.
one or more aqueous resin emulsions and (b)
An antifogging agent composition containing one or more of the two components (a) and (b) of an inorganic colloidal sol, or the two components (a) and (b) above, and a crosslinking agent and/or a liquid dispersion medium. Made by applying an anti-fog composition! 1 Industrial soft vinyl chloride I< +A4 I! It resides in It-y illum.

The present invention will be explained in detail below.

The vinyl chloride resin, which is the main material forming the film of the present invention, includes not only polyvinyl chloride but also copolymers containing vinyl chloride as a main component. Monomers that can be copolymerized with vinyl chloride include vinyl chloride, ethylene, propylene, acrylonitrile, vinyl acetate,
Examples include maleic acid, itaconic acid, acrylic acid, methacrylic acid, but are not limited to these examples.

Vinyl chloride resins can be produced using suspension polymerization, emulsion polymerization, and emulsion polymerization.
The degree of polymerization of the layer for vinyl chloride may be selected from the range of 800''-2500, which may be manufactured by any conventionally known manufacturing method such as suspension polymerization, i8 liquid polymerization, and bulk polymerization. , i: It's a big deal.

The soft vinyl chloride film for industrial use according to the present invention contains at least an ultraviolet absorbing and filtrating acid ester.

The following are listed as extraneous radiation absorbers used in Uni:

2-Ethylhexyl-2-cya/-3,3'-di7-dyl acrylate and ethyl-2-cyano-3,3'-n-7-dyl acrylate, which are cyanoacrylate-based ultraviolet absorbing agents.

2-Hydroxy- which is a benzophenone ultraviolet absorber
4-7toquinbenzo7emene, 2.4-nohydroquinebenzophenone, 2-hydroquine-4-n-octoxybenzophenone, 2-hydroxy-4-7toquine-2'-
Carboxybenzophenone, 2,2゛-Nobidroxy-
4,4'-notoxybenzophenone, 2-hydroxy-4-benzoyloxybenzo7ene, 2,2'-dihydroxy-4-methoxybenzo7ene, 2-hydroquine-4-methoxy- 5-° sulfone benzophenone,
2.2',4.4'-tetrahydroxybenzophenone, 2,2'-nohydroxy-4,4'-notquinbenzo7ene, 2-hydroxy-5-chlorbe, nzophenone, bis-(2-7 4-Hydroquine-5-benzoylphenyl)methane.

2-(2゛-
Hydroxy7enyl)penztrizole, 2-(2'
-Hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5-methylphenyl)
-5-carboxylic acid butyl ester benzotriazole,
2-(2'-Hydroquine-5'-methylphenyl)-5
, f3-nochlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5-ethylsulfonebenztriazole, 2-(2'-hydroxy-5'-
-L-butylphenyl)-5-chloroben/trif/-
2-(2'-hydroxy-5'-t-butylphenyl)bensito+77zole, 2-(2'-hydroxy-
5゜-7mi/phenyl)benzotriazole, 2-(2
'-Hydroxy-3',5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-methylphenyl)-5-7benzotriazole, 2-(2'- methyl-4゛-hydroxyphenyl)
Benzotriazole, 2-(2'-stearyloxy-
3',S'-trimethylphenyl)-5-methylbenzotriazole, 2-(2'-hydroxy-5-carboxylic acid phenyl)benzotriazole ethyl ester 2-(
2'-Hydroxy-3'-methyl-s'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-( 2°-Hydroquine-3゛-
L-butyl-5'-methylphenyl)-5-chlorobenzo) 17azole, 2-(2'-human axy-5''-
methoxyphenyl)benzotriazole, 2-(2'-
Hydroxy-3", 5°-not-butylphenyl)-
5-Chlorobenzotriazole, 2-(2'-hydroxy-5°-cyclohexylphenyl)benzotriazole, 2-(2'-hydroxy-4',5'-tsumethylphenyl)-5-penztriazolebutyl carboxylate Ester, 2-(2'-hydroxy-3',5'-nochlorophenyl)benzotriazole, 2-(2'-hydroxy-4',5'-nochlorophenyl)benzotriazole, 2-(2'- hydroxy-3',5'-tumethylphenyl)-5-ethylsulfonebenzotriazole,
2-(2'-hydroxy-4'-octoxyphenyl)
Benzotriazole, 2-(2'-hydroxy-5'-
metquinphenyl)-5-methylbenzotriazole,
2-(2゛-hydroxy-5゛-methylphenyl)-5
-Carboxylic acid ester benzotri7zole, 2-(2°
-7Setkin-5'-methyl7enyl)benzotriazole.

Among the above-mentioned ultraviolet absorption abrasions, it is preferable to use benzophenone ultraviolet absorption abrasion or benzotriazole ultraviolet absorption abrasion.

These ultraviolet m absorbers can be used in 1!1t or in combination of two or more, and the amount used is 0.01 to 5 parts by weight per 100 parts by weight of vinyl chloride resin, preferably Q, 05. - 2 parts by weight. If the amount used is too small, the desired effect of improving the anti-fog durability will not be obtained, and if it is too high, the effect of improving the anti-fog durability will not be noticeable considering the amount used, and the UV absorption will be reduced by the film. This is not preferable because it bleeds onto the surface and reduces the transparency of the film.

In the present invention, the inclusion of ultraviolet absorbing abrasive in the vinyl chloride 8[1 film] means that υ(UV) is added to the film forming surface in advance and this mixture is made into a film or after the film is formed. Refers to a film whose surface has been coated with an ultraviolet absorbing coating.

When coating the surface of the latter substrate film, an ultraviolet absorbing agent may be added to the coating film components and applied.

It is also possible to use both methods of blending ultraviolet absorbing abrasion into a film specific gravity paste (a method of blending it into a fat composition and a method of applying it after film formation) as described above.

The organic phosphoric acid esters contained in the film of the present invention include triisopropylphenyl phosphate, isodicyldiphenyl phosphate, triphrenol phosphate,
Tris (impropylphenyl) phosphate, tributyl phosphate, ) ethyl phos7ate, trioctyl phos 7 eth, tributoxyethyl phos 7! −),
) Riphenylphos 7ate, Octylnophenylphos 7
ate, ) lyxylenyl phosphate heptaate, etc. Among them, trifrenol phosphate and tricylenyl phosphate are particularly preferred.These are generally plasticizers for vinyl chloride resins and improve the weather resistance of the film. These organic phosphoric acid esters can be used singly or in combination of two or more, and the amount used is vinyl chloride L (90.5 parts per 100 parts by weight of fat, preferably 1 to 10 parts by weight). 7@Denbu.If the amount used is too large or too small, the desired effect of improving antifogging durability cannot be obtained.

The agricultural vinyl chloride υ (fat film) according to the present invention may contain various additives conventionally used for vinyl chloride resins, if necessary.

For example, about 30 to 60 parts by weight of a liquid plasticizer can be added to 100 parts by weight of vinyl chloride O (fat).Furthermore, other resin additives may be added as necessary, such as lubricants, heat stabilizers, and antioxidants. , a stabilizing aid, an antistatic agent, an antistatic agent, an antifungal agent, an antialgal agent, a coloring agent, 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, liquid paraffin, organic acid 4-4 salt, fi7t sphite compound, β-nogaton compound, piperinone. Examples include Hingudo amine compounds of the series.

The above various resin additives can be used alone or in combination.

The amount of each of the above f1 resin additives added is within a range that does not deteriorate the properties of the film, usually 100% of the vinyl chloride resin of the base material.
It can be selected within the range of 5 parts by weight or less.

To blend the ultraviolet absorption resistant and n17-acid ester resin additives into the vinyl chloride PS resin ff1t, which is the base of the film, weigh the necessary amounts of each, and add Ribbon Blengu, Panparimiq+-, and Super Mixer. A conventionally known 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-
(including Gouy method, inflation method), calendar molding method, solution casting method? P: etc.

The film thus formed is coated with another film on the side of the film that is not coated with the anti-fog 1ffl coating film according to the present invention, in order to improve the dust-proofing properties, anti-fog properties, weather resistance and anti-blocking properties of the film. ILII? ? For example, it is possible to provide a coating M made of acrylic resin, 7-fiber resin, or polyolefin resin. Furthermore, it is also permissible to include the above-mentioned ultraviolet absorbing material in this coating layer. Needless to say.

Prevention J! # Hydrophobic acrylic Q (Mairi) which is a component of the agent composition is 10 to 1 (10
@ ji% of alkyl esters of acrylic acid or methacrylic acid [hereinafter, this will be abbreviated as (meth)acrylic acid alkyl ester lid. ], or a mixed monomer consisting of (meth)acrylic acid alkyl esters and alkenylbenzenes, and 0 to 1% by weight of a,β-ethylenically unsaturated' which can be copolymerized with the monomer described above. It is a copolymer obtained by emulsion polymerization of Lt-form and Lt-form in an aqueous medium in the presence of a surfactant.

Examples of the (meth)acrylic acid furkyl esters used in the present invention include methyl acrylate, ethyl acrylate, rhoprovil acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and acrylic acid. decyl acid, methyl methacrylate,
Examples include ethyl methacrylate, rhoprovir methacrylate, impropyl methacrylate, Fa-n-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, etc. Generally, the number of carbon atoms in the alkyl group is 1.
-20 acrylic acid fullyl 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 ebastyrene, a-methylstyrene, vinyltoluene, and the like.

It consists of a mixture of alkenylbenzenes and (meth)acrylic acid alkyl esters! It jt
When using the body, add α in addition.

Although it varies depending on the use of the β-ethylenically unsaturated electrolyte, it is generally recommended that the proportion of (meth)acrylic acid alkyl ester used be 10% by weight or more. In addition, it is desirable that the alkenylbenzene is contained in a range of 70% by weight or less.

The hydrophobic acrylic resin of the present invention has the above-mentioned (meth)
A monomer consisting of a mixture of acrylic acid alkyl esters or (meth)acrylic acid furkyl esters and alkenylbenzenes is contained in a total of at least 60% by weight of the total 111-mer to be polymerized, and 60% by weight If it is less than the weight, the water resistance of the formed coating film will not be sufficient (a) It will not be possible to maintain the anti-fogging performance.

Other copolymerizable α,β-ethylenically unsaturated 11jfit bodies used in the present invention are, for example, α,β-ethylenically unsaturated 11jfit bodies such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, etc. - ethylenically unsaturated carboxylic acid head; a,β-ethylenically unsaturated sulfonic acids such as ethylene sulfonic acid; 2-acrylamide-2
-Methylpropanoic acid; α, β-ethylenically unsaturated phosphonic acids; hydroxyl-containing vinyl monomers such as hydroxyethyl (meth)acrylate; acrylonitriles; acrylamide; glycidyl ester (meth)acrylate, etc. be. These monomers may be used alone or in combination of two or more types, and can be used in a weight range of 0 to 40% by weight. If it exceeds 40% by weight, it is not preferable because it reduces the antifogging performance.

A water-based emulsion of a hydrophobic acrylic tree can be produced by a conventionally known conventional emulsion polymerization method. For example, it can be obtained by emulsion polymerizing the above monomers in an aqueous medium in the presence of a surfactant.

Surfactants used in the production of the hydrophobic acrylic resin in the present invention by emulsion polymerization include anionic surfactants, cationic surfactants, and nonionic surfactants as listed below. .

Examples of anionic surfactants include fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzenesulfonate and sodium flukylnaphthalenesulfonate; 7-alkylbenzene sulfonate; 7-talene sulfonic acid formalin combination; noalkyl sulfosuccinate; There are sulfate salts, etc.

Examples of cationic surfactants include ethanolamines; amine salts such as laurylamine acetate, trimethal-7-l-7minemonostearate)-Y salt, and stearamide ethylnoethylamine acetate; lauryltrimethylammonium chloride; stearyltrimethylammonium chloride, nolaurylnomethyl7ammonium chloride, nostearylnomethylammonium chloride, lavalylnomethylbenzylammonium chloride,
Examples include quaternary ammonium salts such as ste7lylnomethylbennolammonium chloride.

Examples of nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl 7-ether, polyoxyethylene Polyoxyethylene furkylaryl ethers such as nonylphenol; polyoxyethylene esters such as polyethylene glycol monostearate; polypropylene glycol ethylene chloride adducts; polyoxyethylene rubitan monolaurate, polyoxyethylene sorbitan Examples include polyoxyethylene sorbitan fatty acid esters such as monostearate; esters; cellulose ethers, and the like.

These may be used alone or in combination, but there are restrictions depending on the inorganic material used. In other words, the combination of silica sol and cationic surfactant, which generally have a positive charge in an aqueous solution, and anionic surfactant and alumina sol, which generally has a positive charge in an aqueous solution, should be avoided. These combinations tend to cause sol delification and agglomeration/separation of the antifogging agent composition, making application difficult.

These surfactants are 0% based on the total amount of monomers charged.
．． It comes off when used within the range of 1 to 710 weight and 1%.

If it exceeds 10% by weight, the water resistance of the dried coating film will decrease, which is not preferable.

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

These are 0.1 to 10% of the total amount of monomers charged.
It can be used within the mffi% range.

In the polymerization method for obtaining the hydrophobic acrylic resin of the present invention, the monomers may be charged in a batch manner or in a continuous feeding manner.Also, a portion may be polymerized first, and then the remaining portion may be added continuously. It may also be possible to send the data to

Although the monomers to be continuously fed may be fed as they are, it is extremely preferable to feed the monomers as a monomer dispersion using water and a surfactant.

The water-based emulsion of the hydrophobic acrylic resin that is a component of the antifogging agent composition used in the present invention is the water-based emulsion obtained by the above-mentioned emulsion polymerization (as is).
Alternatively, it may be diluted by adding a liquid dispersion medium as described below.Alternatively, the polymer produced by the emulsion polymerization as described above may be collected separately and added to the liquid dispersion medium. It may also be redispersed into an aqueous emulsion.

The hydrophobic acrylic resin used in the present invention must have a glass transition temperature (Tg) within the range of 35 to 80°C. In addition, the Tg resin is based on the type of monomer used and the amount used (compounding amount) (the Tg of the fat is 8
If the temperature exceeds 0°C, a transparent and uniform coating film cannot be obtained (and if the Tg is less than 35°C, the inorganic floid particles tend to aggregate several times and become non-uniformly dispersed, resulting in a non-uniform coating). Since the adhesion of the 8! quality colloidal particles to the coated substrate is insufficient, the 8! quality colloid particles fall off from the substrate surface over time, resulting in poor antifogging performance.

The free colloidal sol, which is the active ingredient of the resist dye MlJ & product used in the present invention, is a hydrophobic vinyl chloride-based tj (Jll
By applying it to the film surface, it functions to impart hydrophilicity to the film surface.

No 8! As a colloidal sol, for example, inorganic aqueous floid particles such as silica, alumina, water-insoluble lithium silicate, iron hydroxide, tin hydroxide, titanium oxide, barium sulfate, etc. can be dispersed in water or a hydrophilic medium by various methods. In addition, C7 includes aqueous sols. Among them, silica sol and alumina sol are preferred. The two spatulas may be used alone or in combination.

The inorganic colloidal sol used preferably has an average particle size in the range of 5 to 100 microns, and two or more types of colloidal sols having different average particle sizes may be used in combination. If the average particle diameter exceeds IQOmμ, the coating film becomes white and devitrified, which is not preferable. Further, if it is less than 51μ, the inorganic colloidal sol may lack stability, which is not preferable.

The inorganic colloidal sol has a solid content weight ratio of acrylic in an amount of 1. It is preferably in the range of 0.5 to 4 with respect to H4 fat. If it is less than 0.5, the effect that prevents light cannot be activated. If it exceeds 4, not only will the anti-fog effect not improve in proportion to the amount of the compound, but if the film is transparent, the coating film that is formed after application will become cloudy and the transmittance of light #a will decrease. This is undesirable because it lowers the surface area, and the coating film tends to become rough and brittle.

When a crosslinking agent is further added to the antifogging agent ML oxide used in the present invention, water resistance is further improved. That is, this crosslinking agent allows the acrylic Q (fats) to form a structure, thereby improving water resistance.

Examples of crosslinking agents used for the purpose of Among them, amine compounds, 7-nolinone compounds, and epoxy compounds are particularly preferred.

The above amine compounds include Noethylenet'J 7
Aliphatic polyamines such as amine, triethylenepentamine, hexamethylene diamine; 3,3'-tumethyl 4,4
rre cyclic amines such as '-diami/nocyclohexylmethane and inphoronoamine; aromatic amines such as 4,4'-noaminediphenylmethane and +s-phenylenenoamine are used.

In addition, as the anoridine compounds described in 1-, tris-2
,4,6-(1-anolyshel)-1,3,S-triazine, trinotyrolpropane-triβ-afrinonylprobionate,)lis[1-(2-methyl)afrinonyl 1-phosphine oxyto, hexa[ 1-(2-methyl)-7 dilinonylcotriphos 77 trianone and the like are used.

Examples of epoxy compounds include reaction products of bisphenol A or bisphenol F and epichlorohydrin, and epoxidized/borac resins produced by the reaction of epichlorohydrin with resin reaction products of phenol (or substituted 7 esters) and formaldehyde. Above, epichlorohydrin and aliphatic polyhydric alcohols such as glycerol, 1
．． Resins obtained by epoxidation using peracetic acid and resinous reaction products produced from 4-butanol, poly(oxypropylene)glyfur or similar poly(IIIifurcol components) are used. Among the epoxy compounds, Furthermore, it is preferable to use tertiary amines or quaternary ammonium salts in combination as a catalyst.

These crosslinking agents can be used in an amount of acrylic a (0.1'u30% by weight based on the fat solids content).A range of 0.5 to 10% by weight is particularly preferable.

The liquid dispersion medium added to the antifogging agent composition used in the present invention includes hydrophilic or water-miscible solvents containing water; water; monohydric alcohols such as methylfurfur, ethyl alcohol, and isopropyl alcohol; ] Examples include polyhydric alcohol heads such as ethylene glyfur, diethylene glycol, and glycerin; cyclic alcohol heads such as bennor alcohol; selon rub acetates; ketones, and the like.

These may be used alone or in combination, but the dispersion stability of the antifogging FF'JJfl composition used in the present invention, the wettability after coating on the film surface, the difficulty in removing the liquid dispersion medium, and the economical efficiency. It is preferable to decide by painting.

The anti-J3 Qiq composition used in the present invention may further contain conventional additives such as antifoaming agents, surfactants, plasticizers, nPA auxiliaries, thickeners, pigments, and pigment dispersion QQ compositions, if necessary. can be mixed.

The antifogging agent composition used in the present invention can be applied to the surface of a vinyl chloride resin film and subjected to forced drying or natural drying to cause continuous failure of the liquid dispersion medium.

As a forced drying method, hot air drying method, infrared radiation method, etc. can be adopted. 6 The heating temperature during forced drying is determined by the applied antifogging agent composition, but it is usually 50°C.
~250"C, preferably 70"-20
It is in the range of 0°C.

In order to apply the antifogging agent composition used in the present invention to the film surface, a method known per se such as a roll foot method, a dip foot method, a brush coating method, a spray coating method, a bar code method, a Ny7co F method, etc. can be used. It may depend on the method.

After applying the anti-gI agent composition to the surface of the film and drying the liquid dispersion medium, the amount of solid matter adhered is usually 0.0.
1-10g/1112, preferably 0.1-5g/I6
The ffl range is 2.

If the adhesion between the film surface and the coating derived from the antifogging ml parabolite used in the present invention is not sufficient, the film surface may be subjected to plasma treatment or the like before applying the anti-gI agent composition. The surface of the film may be modified by applying corona discharge treatment.

For use in this field, the strength will be non-luminous if it is 1 vinyl chloride-based dry (fat film 77: soil, total) IM: preferred; tl, reverse; If the thickness is too thick, it will be inconvenient to make the film and handle its heat (including cutting, gluing, and spreading composition), so it is usually 0.03 to 0.3.
+aII+, preferably in the range of 0.05 to 0.21.

The agricultural soft vinyl chloride film according to the present invention may be transparent, satin finish, or semi-matte finish, and can be used for covering greenhouses, tunnels, etc.
It can also be used for mulching, bagging, etc.

(Effects of the Invention) The present invention has the following particularly remarkable effects, and has extremely great industrial utility value.

(1) The agricultural soft vinyl chloride resin film according to the present invention has extremely excellent water resistance due to the coating film made of a hydrophobic acrylic (3) deafening coating containing fat.

(2) The agricultural soft vinyl chloride resin film according to the present invention has a coating film consisting of a non-refined colloid and has excellent non-stick properties, surface hardness, and water resistance. I'm lost.

(3) Invention 1 Agricultural grade vinyl chloride I;
The oil film is made of an acrylic resin with a specific composition with a glass transition temperature in the range of 35 to 80°C and a colloidal sol. Because it has a coating film, it exhibits extremely excellent antifogging properties, and exhibits stable antifogging properties even under high temperature and high humidity conditions. Furthermore, the vinyl chloride-based tHfrft film as the base material contains ultraviolet absorbing material and an organic phosphate ester, so that the anti-fog performance of the anti-fog coating film of the present invention can be maintained for a long period of time.

(Examples) Hereinafter, the present invention will be explained in detail based on Examples.
The present invention is not limited to the following example 1 unless the gist thereof is departed from.

Examples 1 to 8, Comparative Examples 1 to 9 (1) Preparation of base film Polyvinyl chloride (p=1400) 100 gw octyl 7 talate 45 Epoxy? jl
fat (product name 1'-EP-828J, manufactured by Shell Chemical)
1 Barium-zinc composite stabilizer
1,5 Barium stearate 0.
2 Zinc stearate 0.4 N
Sorbitan more stearamide) 1.5 / ethylene bisstearamide 0.1 〃 is the basic composition,
Furthermore, ultraviolet absorbing and organic phosphoric acid esters shown in Table 1 below were added to this in a formulation of 721 parts shown in the same table.

Each formulation was mixed for 10 minutes using a super mixer, then kneaded for 7 minutes on a roll heated to 165°C, and
Films with thicknesses of 0 and 1 +ata were produced using a - type calendering device.

(2) Preparation of anti-fog M composition Two parts of polyoxyethylene lauryl ether and 80 parts by weight of water were placed in a four-piece flask, heated to 60°C under a nitrogen stream, and then 0.5 parts of ammonium persulfate was added. 100 parts by weight of a mixture of each monomer shown in Table 111 was added dropwise over 3 hours. At this time, the reaction temperature is maintained in the range of 60 to 70°C, but after the completion of the dropwise addition, the reaction temperature is maintained in the same temperature range for 2 hours, and then the mixture is neutralized with cold JJ and aqueous ammonia. I got it. The glass transition temperature of each resin was as shown in Table 1.

The thus obtained acrylic type 0 (fatty emulno a) was blended with j!lIi rocky colloidal sol and others in the species and amounts shown in Table 1 to prepare various antibacterial + m compositions. However, as a comparative example, an antifogging agent composition was also prepared in which no inorganic colloidal sol or acrylic L-leaf was blended.

(3) Formation of a coating film using the (2) inhibitor composition on one side of the vinyl chloride layer film obtained in (1).
) The various antifogging agent compositions obtained in (1) were applied by the barcode method so that the coating amount after drying was 0.5 g/m2 as a solid content, and the mixture was heated in hot air at 90'C for 1 min. The solvent was evaporated by distillation.

(4) Vinyl chloride? j(m Film Evaluation) The vinyl chloride resin film obtained in (3) was evaluated for various properties using the methods described below.

■ Paint film adhesion Cellophane tape was adhered to the @pf;- formed surface of the 3 film, and when the cellophane tape was peeled off, the peeling status of the paint film was observed internally6. The results are shown in Table 1. show. This evaluation standard is the same as for dogs.

○...The paint film is completely intact (it does not peel off and remains completely).

Qx: 2/3 or more of the coating film remained without peeling off.

△... After 273 of the coating film, the heat peeled off.

×...The paint film was completely peeled off.

(2) Flexibility test of coating film Each film was cut into pieces of 5 cm width and 15 cIfi length, and folded back alternately at intervals of 2c+n in a direction perpendicular to the length direction. In this state, a load of 2 to 2 was applied, and 2 was left in a constant temperature bath kept at 15° C. for an hour.

Then, the load was removed, the folds of the film were stretched out, and the appearance of the film was observed internally.

The results are shown in Table 1. The evaluation base formula in this test is as follows.

○: No change is observed in the coating at the crease.

○: Slight cracks are observed in the coating at the creases.

Δ: Some cracks are observed in the coating at the creases.

×: 79721 distinctly observed in the film at the crease.

■ Anti-fogging test Each film was placed in a small tunnel (width I11, depth 4, Mukutori 0.5111) installed in a test field in Ama District, Aichi Prefecture, with the coated side inside the tunnel. Anti-fogging properties were periodically evaluated with the naked eye. The evaluation criteria are as follows.

◎ ...Water adheres in a thin film and no water droplets are observed.

○...Water adheres to the T1 film, but slightly large water droplets are observed.

○X...Water is attached in a thin film, but large water droplets are observed to be attached in some areas! ! ! .

△: Condition in which fine water droplets are observed to be attached in some areas.

×: Fine water droplets are observed on the entire inner surface of the film.

The following is clear from Table 1.

(1) The agricultural soft vinyl chloride resin film of the present invention has excellent anti-fog properties, especially long lasting anti-fog properties, and even after 24 months, it still maintains good anti-fog properties at the initial stage of expansion. There is.

(2) Even if the anti-fogging composition of the present invention is applied, will the vinyl chloride resin film that is the base film still absorb ultraviolet light? If fi IJ acid ester is not included at the same time, the antifogging durability will be poor.

(Comparative Examples - 1, 2, 8) (3) Acrylic U contained in the anti-scratch material (if the glass transition temperature of the material is less than 35°C, the anti-fog durability is poor.
Comparative Example 3) On the other hand, when the glass transition temperature is 80° C. or higher, the adhesion of the anti-fog coating to the flexible film is poor and the anti-fog durability is also poor. (Comparative Example-4) (4) The (meth)acrylic acid Ql mer component constituting the hydrophobic acrylic i/S resin contained in the antifogging agent composition is f30
If the amount of other a, β-ethylenically unsaturated monomer components that can be copolymerized with ffiJft% exceeds 40% by weight, the adhesion of the anti-S coating film to the film will be poor and the anti-fogging duration will be poor. Sex is also inferior. (Comparative Example-5) (5) Antifogging agent composition was N
It consists of two ingredients, acrylic Mtj4 fat and nothing? j! If either one of the quality colloidal sol is lacking, the antifogging properties will be very poor.

(Comparative example-6, 7)

Claims (1)

[Claims] (1) On one or both sides of a soft vinyl chloride resin film containing ultraviolet absorption and organic phosphate ester, (a) acrylic or a monomer consisting of 60 to 100% by weight of alkyl esters of acrylic acid or methacrylic acid. A mixed monomer of alkyl esters of acid or methacrylic acid and alkenylbenzenes and other α,β-ethylenically unsaturated monomers that can be copolymerized with 0 to 40% by weight of the above monomers. (b) one or more aqueous emulsions of hydrophobic acrylic resins having a glass transition temperature in the range of 35 to 80°C obtained by emulsion polymerization of (b) one or more inorganic colloidal sol ( a)
and (b) an antifogging agent composition containing two components or the above (a)
) and (b) An agricultural soft vinyl chloride resin film coated with an antifogging agent composition containing two components, a crosslinking agent, and/or a liquid dispersion medium.