JPS60120739A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PURPOSE:The titled film which can exhibit an antifogging effect for a long period, prepared by forming a film of an ultraviolet ray-curable urethane acrylate coating composition on one surface of a vinyl chloride resin film containing a plasticizer and a specified antifogging agent. CONSTITUTION:A film is formed from a mixture comprising 100pts.wt. (A) vinyl chloride resin, 20-60pts.wt. (B) plasticizer and 1-5pts.wt. antifogging agent comprising a mixture of higher fatty acid/polyalcohol partial esters (diester content of 20-80wt%, and total content of monoesters and triesters of 80-20wt%) obtained by esterifying a hexahydric alcohol obtained by reducing a saccharide (hexose), hexitol, and/or a polyhydric alcohol obtained by removing one or two water molecules from such an alcohol with a higher fatty acid (e.g., palmitic acid). One surface of this film is coated with an ultraviolet ray-curable urethane acrylate coating composition to form a film of a thickness equal to 1/10 or below of that of the base film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agricultural vinyl chloride resin film, and more specifically, it improves the deterioration of anti-fogging properties caused by long-term outdoor expansion, and provides long-term anti-fogging properties. This invention relates to an agricultural vinyl chloride resin film that exhibits a clouding effect.

In recent years, farmers cultivating useful plants have widely adopted a method of promoting or suppressing cultivation of useful plants in greenhouses (warm 1) or tunnels for the purpose of improving profitability.

As for the covering material of Murokono House (warm) or tunnel,
Polyethylene film, ethylene-vinyl acetate copolymer film, polyester film, polycarbonate film, vinyl chloride thread resin film, glass, etc. are used.

Among them, vinyl chloride resin films have better light transmittance, heat retention, mechanical strength, and
It is widely used because it is the best overall in terms of durability, workability, economy, etc.

However, when using a soft vinyl chloride resin film as a covering material for greenhouses or tunnels, moisture that evaporates from the soil or cultivated plants causes water droplets to adhere to the inner surface of the film, making it opaque. The water that reflects the water and blocks its transmission impairs the growth of cultivated plants, and condensed water droplets fall onto cultivated plants, causing disease and quality deterioration.

In order to improve the above-mentioned drawbacks, 1. In order to impart hydrophilicity to the surface of a synthetic resin film, a method is widely used in which a so-called antifogging agent is added to the base resin (for example, in Japanese Patent Publication No.
-3372 publication.

Tokko Sho Rido-3/2G♂ Publication, Tokko Sho 31-39 Ne No. Publication, Tokko Sho J-, 2-2t632 Publication, Tokko Sho!
! (Refer to Publication No. 3/9G, etc.). However, it exhibits anti-fog properties even in the low-temperature period of winter, and the anti-fog agent contained in the film does not get extracted and washed away even during the high-temperature period of summer, resulting in excellent anti-fog effects over a long period of time. There was nothing to show for it.

On the other hand, in order to prevent the antifogging agent contained in agricultural plastic film from migrating to the film surface (outside of the greenhouse or tunnel), there is a method in which an acrylic resin film of a specific composition is entirely formed on the surface of the film (for example, Tokuko Akira θ-
3//9. ! ;Refer to the publication number. ) has been proposed and put into practical use.

However, since the film formed on the base film in this method is a thermoplastic resin, the antifogging agent migrates through this film to the film surface during the summer when the outside temperature is high.
It is difficult to completely prevent the film from running away, and there are still problems in using the film by spreading it out and exposing it outdoors for a long period of time.

Under such circumstances, the inventors of the present invention have conducted intensive studies with the aim of providing an agricultural vinyl chloride resin film that exhibits an antifogging effect even when used outdoors for a long period of time.
This invention has now been fully completed.

Therefore, the gist of the present invention is to provide 700 parts by weight of vinyl chloride resin, a plasticizer, parts by weight of ao-to, dihydric alcohol (hexinotol) obtained by reduction of sugars (hexose), and/or or a higher fatty acid polyhydric alcohol partial ester mixture obtained by esterifying a polyhydric alcohol obtained by separating 7 to 2 molecules of water from these alcohols and a higher fatty acid as raw materials I), and a diester The content ratio of 1θ~l
An antifogging agent whose total content of monoesters and triesters is from 0 to 20% by weight! Contains parts by weight.

Formed into a film, a coating derived from an ultraviolet curable urethane acrylate coating composition is formed. The antifogging agent blended into the (A) higher fatty acid polyhydric alcohol partial ester mixture and (BJ (AJ) the alkylene oxide-added higher fatty acid polyhydric alcohol moiety having a chemical structure in which the acid component alkylene oxide is fully added. ester mixture,
This film is characterized in that a coating derived from an ultraviolet curable urethane acrylate coating composition is formed on one side of the film. The present invention resides in an agricultural vinyl chloride resin film (second invention).

J or T-valve too 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, propylene, 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.

In order to impart flexibility to the agricultural vinyl chloride resin film according to the present invention, 20 to 60 parts by weight of a plasticizer is added to 100 parts by weight of the base resin. The blending amount of the plasticizer is within the above range so that the target film exhibits excellent flexibility and mechanical properties.

Examples of plasticizers that can be used in the present invention include phthalic acid derivatives such as di-n-octyl phthalate, di-λ-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, didodecyl phthalate, and didodecyl phthalate; diisooctyl phthalate; Isophthalic acid derivatives such as di-n-butyl adipate, adipic acid derivatives such as dioctyl adipate;
Maleic acid derivatives such as maleate - Citric acid derivatives such as n-butyl citrate; Itaconic acid derivatives such as monobutyl itaconate; Oleic acid conductors such as butyl oleate; Noricinoleic acid such as glycerin monolysylte Derivatives: Other tricresyl phosphate, epoxy/
Examples include chemical oils and epoxy resin plasticizers.

In the present invention, sugars (
hexahydric alcohol (hexisotol) obtained by reduction of hexahydric alcohol (hexose) and/or 7
-A higher fatty acid polyhydric alcohol partial ester mixture obtained by esterifying a polyhydric alcohol obtained by separation of two molecules of water and a higher fatty acid as raw materials, comprising monoesters, diesters and triesters. (7th invention).

Furthermore, the above CA) higher fatty acid polyhydric alcohol partial ester mixture;
(2nd invention) In the present invention, polyhydric alcohol is a hexavalent alcohol obtained by reduction of sugars (hexose). Alcohol (hexintol), polyhydric alcohol (hexital) obtained by the separation of 7 molecules of water from hexisotol, and polyhydric alcohol (hexit) obtained by the separation of 7 molecules of water from hexitane.These polyhydric alcohols are: It may be a single type, a mixture of multiple alcohols in the same range, or a mixture of alcohols in different ranges.

Specific examples of hexitol among the above-mentioned multi-110 alcohols include sorbitol, mannitol, iditol, talitol, dulcitol, and allodulcitol. Can be mentioned. Specific examples of hexitane include sorbitan, mannitane,
Examples include izintane, taricun, dulcitol, allodulcitol, and the like. Examples of the four hexins include norbite, mannindo, ijitsudo, talitudo, zulsit, and allozursit.

Among the above polyhydric alcohols, sorbitol, sorbitol, sorbitol, sorbitol, sorbitol, and mannitol! All polyhydric alcohols (mannite, mannitan, mannisod) obtained by esterifying them with higher fatty acids,
When blended into a synthetic resin film, the antifogging effect and antifogging durability become particularly excellent, which is particularly preferable.

As the higher fatty acid to be subjected to the esterification reaction with the polyhydric alcohol, a fatty acid having 72 to -2-2 carbon atoms is suitable. Specifically, lauric acid, myristic acid, palmitic acid, and stearic acid.

In addition to fatty acids such as behenic acid and oleic acid, beef tallow, rapeseed oil, corn oil, soybean oil, cottonseed oil, palm oil,
Mention may be made of sesame oil, linseed oil or mixed fatty acids obtained from these hydrogenated oils. Among them, when the fatty acid is a mixed fatty acid having a weight of more than palmitic acid and/or stearic acid Itθ, the prevention of the synthetic resin film containing the fatty acid polyhydric alcohol ester obtained by esterification with the polyhydric alcohol is improved. cloudy effect.

It has excellent anti-fog durability and is preferably 1%.

When the polyhydric alcohols and the higher fatty acids are reacted to form an ester, (1) all of the hydroxyl groups of the polyhydric alcohol undergo an esterification reaction with the fatty acid; A mixture of three components is obtained: a partial ester in which a portion of the hydroxyl groups of C' is esterified with a fatty acid, and C') an unreacted product.

Among the higher fatty acid polyhydric alcohol partial ester mixture obtained by reacting the polyhydric alcohol and the higher fat, the content ratio f of diesters, 20-♂O weight ratio, monoesters and triesters, A heavy gas mixture having a sum content of ♂0 to 20 by weight is preferable because it provides excellent protection for the film at low temperatures and less decreases in antifogging effect even when the film is exposed to high temperatures. Within the above range (■), the content of diesters in a ratio of 1 cup exceeds the sum of monoesters and triesters by
Particularly preferred.

The agricultural vinyl chloride resin film according to the present invention has a chemical structure in which a part of the above (A) higher fatty acid polyhydric alcohol partial ester mixture is added with an alkylene oxide having a chemical structure in which (BJ i (AJ acid component alkylene oxide) is added). It is possible to combine the replacement type b (AJ acid component 03) component with the type higher fatty acid polyhydric alcohol partial ester mixture (second invention).

Alkylene oxides that can be added to higher fatty acid polyhydric alcohol partial esters include ethylene oxide, propylene oxide, polyethylene oxide, phenylene oxide, polyethylene oxide,
Examples include polypropylene oxide and polybutylene oxide.

The above (AJ acid component or (A
) component and FB) component is the total amount of vinyl chloride resin 1
00 parts by weight, the range is 7 to 5 parts by weight. When the amount is less than the above range, the antifogging properties of the resin film are unfavorable, whereas when it is more than the above range, bleed-out occurs on the film surface, which is undesirable.

The base resin constituting the agricultural vinyl chloride resin fill-in according to the present invention may also contain various conventional resin additives, such as lubricants and heat stabilizers, if necessary.

Antistatic agents, ultraviolet absorbers, pigments, dyes, etc.

Examples of the agent or heat stabilizer include polyethylene wax, bisamide, stearic acid, zinc stearate,
Examples include barium stearate, calcium stearate, barium ricinoleate, and the like. Examples of the ultraviolet absorber include Henzo I-1) azole yarn, benzoate type, pentuphenone type, cyanoacrylate yarn, and phenylpuri/late yarn. still,
Examples of pigments and dyes include titanium oxide, silica, ultramarine blue, and phthalocyanine blue.

These resin additives may be included in a small amount of 1 part by weight or less per 100 parts by weight of the vinyl chloride thread resin.

The above (AJ acid component or French) is added to the base vinyl chloride thread resin.
In order to blend the components and (B) component, and further include various resin additives 2 if necessary, ordinary blending techniques and mixing techniques such as pump blenders, Banbury mixers, super mixers, and other blending machines and mixing methods are used. This is possible by using a machine.

In order to form the vinyl chloride resin composition into a filtrate, a method known per se may be used, such as the melt valve 1 old method, the solution casting method,
A calendar method or the like may be used.

If the agricultural vinyl chloride thread resin film according to the present invention is too thin, the strength will be insufficient, which is undesirable.On the other hand, if the film is too thick, it will be inconvenient for the film work and subsequent handling. , 03 to 0.3 axillary, preferably θ. It is preferable that θ,j be in the range of −0.2 mn.

The agricultural vinyl chloride thread resin film 11 related to the unexploded surface is formed by forming a coating of an ultraviolet curable urethane acrylate composition on one side of a base film. In the present invention, the ultraviolet curable urethane acrylate coating composition refers to a polymerizable urethane acrylate resin having an unsaturated equivalent (polymer molecular weight/number of polymerizable double bonds in the polymer) of 30θ to 0θ, Consists of possible monomers, photosensitizers, and (if necessary, solvents, coatability improvers, etc.)

The polymerizable urethane acrylate resin used in the present invention refers to polyether polyols and/or polyester polyols, or polyurethane polyols obtained by reacting polyether polyols, polyester polyols, etc. with polyincyanates, which are polyfunctional iso/acrylate resins. Anate compounds and also ethylenically unsaturated compounds with active hydrogen? Obtained by reaction.

Polyether polyols include alkylene oxides (e.g., ethylene oxide, prohylene oxide, etc.).

(e.g., ethylene glycol, /, 2-propylene glycol, /, couptanediol, /, hexanediol, glycerin, trimethylolethane, trimethylol-/L/) and polyols (e.g., ethylene glycol, /, 2-propylene glycol, /, couptanediol, /, hexanediol, glycerin, trimethylolethane, trimethylol-/L/). , /, J to hexanetriol, pentaerythritol, sorbitol, diethylene glycol, triethylene glycol, tetraethylene di-1-nocol, polyethylene glycol, Schiff 80 bire glycol, polypropylene glycol, etc.)
It is obtained by the reaction of

The polyester polyol is a combination of the above polyols and epoxy compounds (e.g., n-butyl glycidyl ether, allyl glycidyl ether, and polycarbon acids (e.g., phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,
Isophthalic acid, terephthalic acid, phthalic anhydride, conorlic acid, adipic acid, azelaic acid, lactic acid, maleic acid, maleic anhydride, fumaric acid, hyporomellitic acid, trimellitic acid, etc., and esters thereof including. )
or by the reaction of the above polyol and polyurethane acid, or the above epoxy compound and polycarboxylic acid.

Nao, Bol) ether), or a polyester polyol containing a glycidyl group and a polymerizable unsaturated carboxylic acid.
It is obtained by reacting with sonic acid (for example, (meth)acrylic acid, etc.).

As the polyfunctional incyanate compound used in the present invention, diincyanates and triisocyanates are particularly preferable, such as tetramethylene diisocyanate, hexamethylene diisocyanate, co,cutolylene diisocyanate, λ,otolylene diisocyanate, diphenylmethane, diisocyanate,
Examples include inphorone diincyanate, lysine diisocyanate, modified diisocyanates thereof, and hydrogenated diisocyanates, and these may be used alone or in combination of two or more.

Examples of ethylenically unsaturated compounds having active hydrogen include hydroxy group-containing compounds (for example, alino, alcohol,
- monohydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, etc.), amine group-containing compounds (e.g. monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate) ), reaction products of acrylic vinegar or methacrylic acid and monoepoxy compounds (e.g. glycidyl (meth)acrylate, n-butyl glycidyl ether, allyl glycidyl ether, etc.), glycidyl acrylate or glycidyl methacrylate and monocarboxylic acids Examples include reaction products of containing compounds (eg, acetic acid, butyric acid, benzoic acid, etc.), or secondary monoamine compounds (eg, dimethylamine, diethylamine, piperidine, methylaniline, etc.).

The polymerizable urethane acrylate resin obtained by reacting the above compounds has two or more ethylenically unsaturated bonds in the resin skeleton, (polymer molecular weight)/(polymerizable double bond in the polymer). The unsaturation equivalent expressed by number) is 3θO ~
Assume that the angle is θO0. The unsaturation equivalent is less than 300.

Coatings formed from coating compositions containing such resins have insufficient flexibility and are unsuitable. Unsaturation equivalent is ♂θ0
If it exceeds 0, a coating formed from a coating composition containing such a resin will not be sufficiently cured and will stick, resulting in problems in use. The unsaturation equivalent is -10 in the above range
A range of 0 to θθO is suitable.

In the present invention, monomers that can be polymerized with the polymerizable urethane acrylate resin include styrene, vinyl toluene/,
Styrene compounds such as t,7-butylnutine, monochlorostyrene, α-methylstyrene, p-methylstyrene, and divinylbenzene; Vinyl esters such as vinyl acetate, vinyl benzoate, vinyl butyrate, and vinyl benzoate; Noenoxyethyl (meth)acrylate, Isodecyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, ethoxy (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, acrylic ( Meta)
Acrylate, co-hydroxyethyl (meth)acrylate, co-hydroxypropyl (meth)acrylate, co-hydroxypropyl (meth)acrylate, co-methoxyethoxyethyl (meth)acrylate, benzyl (
meth)acrylate, cyclohexyl (meth)acrylate, -monohydroxyethyl (meth)acryloyl phosphate, tetrahydrofurfuryl (meth)acrylate, /, 3-butanediol di(meth)acrylate, /, couptanediol di(meth)acrylate acrylate%
/, Otsu-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate (meth)acrylate compounds such as (meth)acrylate, 3-methylpentanediol di(meth)acrylate, trimethylolglopane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; unsaturated nitrile compounds such as acrylonitrile;
α,β-unsaturated amides such as acrylamide and N-butoxymethylacrylamide; diethyl fumarate,
Examples include diester compounds of unsaturated polycarboxylic acids such as dibutyl maleate. These may be used alone or in combination of two or more.

The blending ratio of the polymerizable urethane acrylate resin and the monomer that can be polymerized with it is such that the coating formed after a small amount of the latter is too brittle.

Undesirable. The preferred blending ratio is that the blending ratio of the polymerizable phletane acrylate resin and the monomer that can be polymerized is such that the former is greater than or equal to θ~? The ratio of 2 to the latter is 60~/(the total amount of both is 100), and particularly preferred is Zθ~? θ vs. gθ~/θ (total amount of both f
700).

In the present invention, a photosensitizer is blended so that the coating composition containing the polymerizable urethane acrylate resin and a monomer polymerizable therewith preferably undergoes a curing reaction by being fully irradiated with ultraviolet rays.

In the present invention, photosensitizers include benzoin, benzoin methyl ether, benzoylpropyl ether,
Penzoyl phthyl ether, benzoyl phenyl ether, anthraquino/.

Naphthoquinone, benzophenone, benzoyl peroxide, benzyl ketal, /, /-dichloro1'roacetophenone, para-t-butyldichloroacetophenone, 2
-chlorothioxanthone, co-diethoxyacetophenone, Michler's ketone, 2,2-dichloro-couphenoxyacetophenone, phenylglyoxylate,
Examples include α-hydroxyisobutylphenone, N-methyldiethanolamine, and triethylamine.

If the amount of photosensitizer is too small, curing will be insufficient even when irradiated with ultraviolet rays, which is undesirable.On the other hand, if it is too large, there will be no difference in curability even if the amount is increased, which is undesirable. . The preferred distribution amount is θ, O/~20g%, preferably 0.0% based on the total amount of the three components: the polymerizable urethane acrylate resin, the monomer that can overlap with these, and the photosensitizer.
It is selected from the range of 7 to 10% by weight.

An ultraviolet curable urethane coated on the surface of the agricultural vinyl chloride resin film according to the present invention may also be used.

Solvents, coating property improvers, etc. are added for the purpose of coating the coating composition on the film surface, and specific examples include methyl ethyl ketone, methyl imbutyl ketone, and ethyl acetate.

Butyl acetate, ethyl alcohol, Ingropil7 alcohol, toluene, xylene, bi'7. Examples of the coating property improver include silicone surfactants and/or fluorocarbon surfactants.

The above ultraviolet curable urethane acrylate coating composition is
In addition to the above-mentioned components, other substances may be added for the purpose of improving the physical properties of the coating, such as its flexibility.

These substances include polyethylene, polyglopylene,
Polystyrene, polyacrylate, polymethacrylate-1
・Synthetic resins and natural resins such as polyvinyl chloride, polybutadiene, and cellulose, rubbers, prepolymers and oligomers such as diallylphthane polymer and butadiene oligomer, etc.

The film of the present invention is applied to one side of the base film.

An ultraviolet curable urethane acrylate coating composition is applied, and the composition is fully irradiated with ultraviolet rays to completely cure the coating. Any known coating method may be used, such as a curtain roll coating method, a spray V coating method, or a rod coating method.

The agricultural vinyl chloride film according to the present invention is obtained by irradiating a coating composition applied to one side of a base film with ultraviolet rays to cure the coating, as described above. In order to harden the film, it is sufficient to irradiate it with ultraviolet light having a wavelength of 260 to 50,049 microns, particularly preferably a wavelength of 30 θ to 0 mm to cause a curing reaction. A high-pressure mercury lamp is a light source for ultraviolet light of this wavelength.

Medium-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, arc lamps, etc. are used.

In the present invention, the thickness of the cured coating formed on one side of the base film is preferably H, o or F less than the thickness of the base film.

If the Jl of the coating is less than 1/1O of the thickness of the base film, there will be a difference in flexibility between the base film and the coating, and phenomena such as peeling of the coating from the base film will easily occur. This is undesirable because cracks occur in the coating and reduce the strength of the base film.

In addition, when forming a hardened film on the surface of a wide and long base film, if a part with a width of /θ~≦θ where no film is formed is provided at both ends in the width direction, When they are stacked on top of each other and bonded using a high-frequency sewing machine, the strength of the bonded surface is improved, which is preferable.

When the agricultural vinyl chloride resin film according to the present invention is actually used as a covering material for a greenhouse or tunnel, the surface provided with the cured film is positioned outside the greenhouse or tunnel and stretched.

The present invention has not only been described in detail above, but also has the following particularly remarkable effects, and its agricultural utility value is extremely large.

(1) The agricultural vinyl chloride resin film according to the present invention contains an antifogging agent with a specific structure, so it exhibits full antifogging properties even in the low temperature period of winter, and provides antifogging properties even during the high temperature period of summer. Since the fogging agent does not seep out significantly and is not washed away, it exhibits excellent antifogging effects over a long period of time.

(2) Since the agricultural vinyl chloride film according to the present invention has a single coating formed on one side, the antifogging agent blended into the film does not ooze out through this coating and remains. It gradually oozes only from the inner surface. Therefore, it exhibits excellent antifogging effects over a long period of time.

(3) The agricultural vinyl chloride thread resin film according to the present invention has a coating derived from the ultraviolet curable urethane acrylate coating composition formed on its surface, which is highly flexible and difficult to peel off. It has excellent weather resistance and is non-adhesive, making it difficult for dust to adhere to it. Therefore, even when used outdoors for a long period of time, transparency can be maintained at a high level.

Hereinafter, the present invention will be explained in detail based on examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example/~Event, Comparative Example/~7 (1) Preparation of basic film Polyvinyl chloride (p-/4700)...100 parts by weight Dioctyl phthalate......
・・・・ Soj tricresyl phosphate ・・
・・・・・・・・・ 5〃Epoxidized soybean oil・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・／
rr barium-zinc composite stabilizer ・・・・・・・・・
・／Barium stearate・・・・・・・・・・・・
... 9o, x tr zinc stearate ...
・・・・・・・・・・・・・・・0Ig r, 2. Hydroxybenzophenone・・・・・・・・・0.3-
A different resin composition was prepared, and all of the types and amounts of antifogging agents shown in Table 1 were added. However, in Comparative Examples/S, it was not blended.

Each formulation was stirred and mixed for /θ minutes using a super mixer, and then kneaded on a mill roll heated to /0°C to prepare a base film having a thickness of 0.7.

(2) Reference example of preparation of ultraviolet curable urethane acrylate coating composition (a) Hexamethylene diisocyanate/B and 1 part by weight (Hereinafter, in reference examples and production examples, field U means "part by weight" ) and θμ part of monomethyl ether hydroquinone were weighed, placed in a flask, and stirred.

While maintaining the internal temperature of this flask at a temperature of 7°C, a total mixture of λ-hydroxyethyl acrylate, 0.63 parts of dibutyltin dilaurate, and 0.2 parts of monomethyl ether hydroquinone was added to the flask. The mixed solution was added dropwise and reacted to obtain a polymerizable double bond-containing isocyanate derivative.

(1) 3-methyltetrahydrophthalic anhydride-・t
ty parts, 292 parts of adipic acid, 2 parts of n-butylcricidyl ether, 0 parts of Epicoat (manufactured by Yuka Shell Epoxy Corporation, epoxy resin), and 90 parts of goubutanediol. I put it in a flask. While stirring the contents of the flask, adjust the internal temperature to /j O,:l:J
'O, and react the product at this temperature until the acid value becomes 6f or less.

A polyester polyol was obtained. To the product obtained in this way, glycidyl acrylate 2j, monomethyl ether nohydroquinone/part, and part part were further added, and the mixture was stirred.

Temperature f73! ±J-°C, and the reaction was carried out at this temperature until the acid value of the product became 10 or less to obtain unsaturated polyester prepolymer Bi.

(OJ incyanate derivative A2 obtained in (a) above,
? ! . 7 parts and 5 parts of the unsaturated polyester blend polyester m-B2.203° obtained in (b) above, put them in a flask, stirred at C and raised the temperature to 103 ± J °C, and the reaction system (220 parts of isophorone diisocyanate and
Monomethyl ether hydroquinone o, .: z parts were weighed and put into a flask. Internal temperature f of this flask: Otsu θ
While raising the temperature to 0° and maintaining it, 7 parts of 2-hydroxyethyl acrylate and 6 parts of dibutyltin dilaurate were added.
! A mixed solution of 0.3 parts of monomethyl ether hydroquinone and 0.3 parts of monomethyl ether hydroquinone was added dropwise and reacted to obtain a polymerizable double bond-containing isocyanate derivative D7i.

Ie) Isocyanate derivative D/nito obtained in (d) above! ,? 1 part and 2.203.3 parts of the unsaturated polyester V polymer obtained in step (1) above were placed in a flask and heated to 106±3°C while stirring to remove Neo in the reaction system. The base concentration is /. The reaction was carried out until the temperature decreased to below the θ coefficient to obtain an ultraviolet curable urethane acrylate resin E having unsaturation equivalents of J, f, and t'.

Production Example/Reference Example 1c) To 0/00 parts of the ultraviolet curable urethane acrylate resin prepared, 30 parts of co-hydroxyglobil methacrylate, <10 parts of pentalythritol triacrylate, 3 parts of benzoyl butyl ether,
20 parts of toluene, FG-3/(manufactured by Thriem, USA, fluorine-based surfactant)/. Two parts were each weighed and mixed to obtain coating composition F.

Production Example λ 0 parts of the ultraviolet curable urethane acrylate resin E prepared in Reference Example (e), 0 parts of tetrahydrofurfuryl acrylate, 3, part o, penzoyl globil ether! parts, toluene 7.5 parts, Brc-ri 3/(
Same as production example/) 7. Weigh and mix each of the two parts,
Coating composition G was obtained.

Production Example 3 %/6 O-hexanediol diacrylate jθ part, penzoyl globyl ether Jj part, F C-g 3/(Production Example /, 2 parts of acrylic resin (manufactured by Mitsubishi Rayon ■, Dianal BR-40) with a solid content of j% in a medium; I got it.

Production Example Weigh 762 parts of hexamethylene diisocyanate and 0.2 parts of monomethyl ether hydroquinone,
Add 23.2 parts of 2-hydroxyethyl acrylate and dibutyl tin dilaure into a flask and raise the temperature to 0°C while stirring, and while maintaining the internal temperature at 40°C = r-°C. 1・θ, Otobe and Monomethyl Niterha Idokuki 2F 0. ．． 2 parts of the mixture are added dropwise and allowed to react;
A urethane acrylate resin having an unsaturation equivalent of 200 was obtained.

To 700 parts of the above urethane acrylate resin, 30 parts of 21-hydroxyglobil methacrylate, θ parts of pentaerythritol triacrylate, 3 parts of benzoin butyl ether, 10 parts of toluene, 3 parts of Fc-g (same as Production Example/) and 0 parts were weighed and mixed to obtain a coating composition 1.

(3) Formation of Coating The coating composition obtained in Production Examples/--G was coated on one side of the base film prepared by the method described in (1) above by gravure coating.

The surface to which this coating composition was applied was heated using a high-pressure mercury lamp (KW?θW).
/α), the substrate film f , 20 m
It was transferred at a speed of 7 minutes to cause a curing reaction and form a 3 micron thick film. However, no film was formed on the films of Comparative Examples/and Yu, and an acrylic resin film was formed on the film of Comparative Example B by the following method.

Comparative Example B Film λ-hydroxyethyl methacrylate, methyl methacrylate, and n-butyl acrylate were polymerized at a weight ratio of /j:, fθ:3j, and the resulting acrylic polymer (molecular weight / Toluene was added to 0.ooo) so that the solid content was 20% to obtain an acrylic resin coating composition.

The above acrylic resin coating composition was applied to one side of the base film prepared by the method described in tFI (1) by gravure coating method, and left in hot air at /30C for 7 minutes to scatter the solvent. , a coating 3 microns thick was formed.

(4) Film evaluation (sword film flexibility test) Cut each film from the width to L length/jm, and cut it into square circles perpendicular to the length direction at intervals of -2 crn. In this state, a 2 kg load was applied from above, and the film was left in a constant Na tank held at /j'O for 2 hours.Then, the load was removed, and the creases of the film were cut. The film was stretched out and the appearance of the film was observed with the naked eye.The results are shown in Table 1.The evaluation criteria in this test are as follows.

(Door: No change is observed in the coating at the 9th fold.

△...Slight cracks are observed in the coating at the creases.

×: Crank is significantly observed in the coating at the 9th fold.

■ Anti-fogging evaluation 72 types of films were installed in a pipe house (frontage 3m, depth jm, ridge height /, j
m, roof slope of 30 degrees) was coated with a coating on the outside of the Mengane House, from February 1939 to 1939! Expansion test for a year until March? It became te.

During the spreading test, the antifogging properties of each ficin were observed with the naked eye over time. The results are shown in Table 7.

The evaluation criteria for "anti-fogging properties" were as follows.

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

○: Water is attached in a thin film, but slightly large water droplets are observed in condition B.

○×・・・Water adheres in a thin film, but large water droplets are observed to be attached in some areas.

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

×: Condition in which fine water droplets are observed to adhere to the entire inner surface of the film.

From Table 1, the following becomes clear.

(1) The film according to the present invention has a thickness of 0. / Despite being thin, it can be used throughout the winter λ season. On the other hand, when commercially available agricultural vinyl chloride film U of the same thickness is used in the winter/season, the antifogging properties are extremely reduced.

(2) If the composition of the higher fatty acid polyhydric alcohol partial ester is within the scope of the claims, the anti-fogging properties and anti-fogging properties of the film (Examples/~l) 1 containing all of these components are excellent. However, if it is outside the scope of the claims, the antifogging properties and antifogging durability of the films containing this (Comparative Examples 3 to G) will not be very good.

When a hardened film is formed on one side (Example/), the antifogging durability is excellent, but when a hardened film is not formed (Comparative Example j), the antifogging durability is poor.

(4) If the higher fatty acid polyhydric alcohol composition is within the claimed range and the type of coating formed on one side of the opening is a hardened coating, the antifogging durability of the film is better. (Example 21 Comparative Example B). Furthermore, the cured coating is derived from a coating composition containing a polymerizable urethane acrylate resin with an unsaturation equivalent weight greater than 300 than that derived from a coating composition containing a polymerizable urethane acrylate resin with an unsaturation equivalent weight less than 300. It is more flexible and exhibits superior anti-fog durability than those derived from natural materials (see Example 2 and Comparative Examples).

Applicant: Mitsubishi Mononando Chemical Vinyl Co., Ltd. Procedural Amendment 2 Name of the Invention: Agricultural Vinyl Chloride Resin Film 3 Relationship with the person making the amendment Patent Applicant Address: 2-1 Shiba, Minato-ku, Tokyo No. 30 Name: Juki Oonima Mitsubishi Monsanto Kasei Vinyl Co., Ltd. 4 agents 100 (and 1 other person) 5 Date of amendment order (=J Voluntary amendment 6 Number of inventions increased by amendment 0 7 Subject of amendment Description Contents of amendment in Column 8 Detailed Description of the Invention (1) In the 520th line of the 1st line of the 2nd line between specifications, ``
The statement that the former has a weight ratio of 99 to 10 to the latter is corrected to ``the former has a weight ratio of 30 to 90 and the latter has a weight of 70.

(2) In the specification, page 2j, line 10 to line 72, “
Penzoyl propyl ether, penzoyl phther ether, penzoyl phenyl ether J are replaced with "benzoin propyl ether, penzoyl phther ether, penzoyl phenyl ether,
Pent-in-phenyl ether,” is corrected.

(3) In the 1st line of page 3 of the specification, [,2,ψ-hydroxybenzoenone] is amended to read ``,2.

(4) In the third line of page 3j of the specification, "3 parts of benzoyl butyl ether" is corrected to "3 parts of benzoin butyl erthyl."

(5) On page 3j of the specification, lines 1 and 2, "2.j parts of benzoylpropyl ether" is amended to "parts of benzoinpropyl ether J."

(6) On page 3j, line 20 of the specification, the text "2.5 parts of benzoylpropyl ether" is color corrected by "2-5 parts of benzoinpropyl ether".

(7) In Specification I, page 37, lines 1g to 1j, the phrase “acrylic resin fill was formed.” was replaced with “
An acrylic resin film was formed. ” he corrected.

that's all

Claims (8)

[Claims] (1) 20 parts of plasticizer per 10 parts by weight of vinyl chloride resin. 60 parts by weight, polyvalent alcohol (hexitol) obtained by reducing sugars (hexose) and/or polyhydric alcohols obtained by separating 7 to 2 molecules of water from these alcohols, and higher fatty acids as raw materials. , is a mixture of higher fatty acid polyhydric alcohol partial esters obtained by esterification, and the content ratio of diesters is 20~r0% by weight 1 The content ratio of the sum of monoesters and triesters is! 7 to 3 parts by weight of an antifogging agent having a weight range of θ to λθ is blended, formed into a film, and a coating derived from an ultraviolet curable urethane acrylate coating composition is formed on one side of the film. PVC resin film for agricultural use. (2) Claim (1) characterized in that in the higher fatty acid polyhydric alcohol partial ester mixture, the content of diesters exceeds the sum of the content of monoesters and triesters. agricultural vinyl chloride resin film. (3) Claims (1) to (2), characterized in that the polyhydric alcohol is nrubisotho (nrubitol) type polyhydric alcohol and/or mannitol (mannitol) polyhydric alcohol tetyl. agricultural vinyl chloride resin film. (4) The ultraviolet curable urethane acrylate coating composition is a polymerizable urethane acrylate resin having an unsaturated equivalent (polymer molecule I/number of polymerizable double bonds in the polymer) of 300 to 20θθ, and is polymerizable with this resin. Agricultural vinyl chloride system according to claims (1) to (3), characterized in that it comprises a monomer, a photosensitizer, and, if necessary, a solvent, a coatability improver, etc. resin film. (5) 700 parts by weight of vinyl chloride resin, 0 parts by weight of plasticizer λO-, (A) hexahydric alcohol (hexitol) obtained by reduction of sugars (hexose)
and/or a higher fatty acid polyhydric alcohol partial ester mixture obtained by esterifying a polyhydric alcohol obtained by separating 7 to 2 molecules of water from these alcohols and a higher fatty acid as raw materials, and a diester The content of monoesters and triesters is 20 to 0% by weight, and the total content of monoesters and triesters is 0. - 2θ weight cracking, and (BJ) an alkylene oxide-added higher fatty acid polyhydric alcohol partial ester mixture having a chemical structure in which an alkylene oxide is added to the above higher fatty acid polyhydric alcohol partial ester mixture; An agricultural vinyl chloride resin film, characterized in that: /~3 parts by weight of the mixture is blended, formed into a film, and a coating derived from an ultraviolet curable urethane acrylate coating composition is formed on one side of the film. . (6) Agriculture according to claim (5), characterized in that in the higher fatty acid polyhydric alcohol mixture, the content of diesters exceeds the sum of the content of monoesters and triesters. Vinyl chloride resin film for use. (7) Claims (5) to (6) characterized in that the polyhydric alcohol is a sorbitol polyhydric alcohol and/or a mannitol polyhydric alcohol. The agricultural vinyl chloride resin film described above. (8) The ultraviolet curable urethane acrylate coating composition contains a polymerizable urethane acrylate resin having an unsaturated equivalent (polymer molecular weight/number of polymerizable double bonds in the polymer) of 30θ to f00θ, and a monomer polymerizable with this resin. chromatin and photosensitizer,
Further, if necessary, claims (5) to (7) include a solvent, a coating property improver, etc.
Agricultural vinyl chloride resin film as described in .