JPS6129263B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, a coating film made of a cellulose ester resin composition containing cellulose ester as a main component is coated with an olefin-based, ester-based, carbonate-based, or vinyl chloride-based resin film containing an antifogging agent (in the present invention, it is referred to as a film). Regarding the anti-fog and dust-proof film for agriculture and horticulture, which has excellent dustproof properties, anti-fog properties, crack resistance, blocking resistance, adhesion to the base film, and heat In addition to improved properties such as sealing performance and curl resistance, it also overcomes the problem of deterioration of anti-fog or dust-proof properties during high temperatures in summer, and is unique in that it exhibits anti-fog or dust-proof effects on both sides even though it is coated on one side. The present invention relates to an anti-fog and dust-proof film for agriculture and horticulture, which has a new type of cellulose ester resin composition coating which exhibits the following characteristics and also has new improved effects such as the effect of preventing rainwater fogging phenomenon. More specifically, the present invention provides the following (i) to (iii), (i) (i) on at least one side of an olefin-based, ester-based, carbonate-based, or vinyl chloride-based resin film containing at least an antifogging agent. from about 50 to about 90%, preferably from about 55 to about 80%, more preferably from about 60 to about 80% by weight, based on the combined weight of (ii) (i) and ( from about 10 to about 50%, preferably from about 20 to about 45%, more preferably from about 20 to about 40% by weight, based on the total weight of ii), of a polymer or copolymer of an alkyl methacrylate ester; and/or at least one methacrylic acid alkyl ester and other comonomers selected from the group consisting of acrylic acid alkyl esters, α-/β-unsaturated fatty acids, acrylic acid epoxidized alkyl esters, and styrenes in subcomponent amounts. and (iii) 0 to about 5% by weight, based on the total weight of (i) and (ii).
The present invention relates to an anti-fog and dust-proof film for agriculture and horticulture, characterized by having a coating film of a cellulose ester resin composition containing an anti-fog agent. The present invention also relates to a coating composition suitable for use in coating an agricultural and horticultural film containing an antifogging agent to make the film an excellent antifog and dustproof film for agricultural and horticultural use. i) to (iv), (i) from about 50 to about 90% by weight, preferably from about 55 to about 80%, more preferably from about 60 to about 80% by weight, based on the total weight of (i) and (ii); % of cellulose esters, (ii) from about 10 to about 50%, preferably from about 20 to about 45%, more preferably from about 20 to about 40% by weight, based on the combined weight of (i) and (ii). A polymer or copolymer of methacrylic acid alkyl ester and/or at least one methacrylic acid alkyl ester and a subcomponent amount of acrylic acid alkyl ester, α-/β-unsaturated fatty acid, acrylic acid epoxidized alkyl ester, and (ii)' 0 to about 20% by weight, based on the total weight of (i) and (ii); (iii) 0 to about 5% by weight, based on the total weight of (i) and (ii);
and (iv) 0 to about 10% by weight, based on the combined weight of (i) and (ii).
The present invention relates to a composition for coating agricultural and horticultural films containing an antifogging agent, which is made of a solvent solution of a cellulose ester resin composition containing a plasticizer. For example, synthetic resin film coverings containing antifogging agents are widely used in agricultural and horticultural greenhouses, tunnels, etc., and the plasticizer migrates to the film surface over time, causing dust to accumulate. As a result, there is a disadvantage that the light transmission property is reduced.Furthermore, along with the migration of the plasticizer, the antifogging agent also migrates to the surface and is washed away, causing the antifogging effect to be lost in a relatively short period of time. There are disadvantages such as the inconvenience of In order to avoid such difficulties, there is also a known proposal to apply a resin coating to at least one side of an olefin-based, vinyl chloride-based, or other synthetic resin film containing at least an antifogging agent to overcome the above-mentioned difficulties. There is. For example, Japanese Patent Publication No. 7061/1973 proposes a coating for soft vinyl chloride resin products. Although this proposal does not specifically mention anti-fog films for agriculture and horticulture, it does address the drawbacks of conventional paints, which have the disadvantage that the plasticizer in these products migrates to the surface or the surface is easily contaminated due to static electricity. In order to overcome this problem, antistatic agents such as cationic quaternary ammonium salts, polyethylene polyamines, and nonionic betaine types are added to the copolymer of methyl methacrylate and butyl methacrylate in a specific monomer weight range. Paints for soft PVC products have been proposed in which 0.1 to 1 part by weight is added. For example, Japanese Patent Publication No. 46-37429 proposes a method for producing a hydrophilic synthetic resin film or sheet in which a resin coating is applied to the synthetic resin film or sheet in order to impart hydrophilicity to the film or sheet. Similar to the above proposal, this proposal also makes no mention of antifogging films for agriculture and horticulture, their technical problems, and their solutions. In this proposal, at least one selected from acrylic acid ester polymers or copolymers thereof, vinyl acetal polymers or copolymers thereof, and vinyl alcohol fatty acid ester polymers or copolymers thereof, and a fruit surface active agent such as It has been proposed to coat synthetic resin films and sheets with a mixture of fatty acids and sorbitan esters. Furthermore, Japanese Patent Publication No. 47-28740 proposes a vinyl chloride film for agricultural use. In this proposal, a specific acrylic resin, i.e. hydroxyalkyl (meth)acrylates 15-25
A resin obtained by polymerizing a monomer mixture consisting of 0.5 to 5% by weight of an α,β-unsaturated acid monomer and other (meth)acrylic monomers is applied to one or both sides of a vinyl chloride film. It has been proposed to form a coating by coating. Furthermore, as a proposal similar to the above proposal,
No. 50-5733 describes the method of polymerizing the same monomer mixture as the above proposal in a vinyl chloride resin non-solvent. A coating agent for a soft or semi-rigid vinyl chloride resin containing the following has been proposed, and the application of this coating agent to a film for agricultural chemicals has also been described. In addition, Japanese Patent Publication No. 31195/1983 describes an antifogging agent that limits the migration of the antifogging agent to the film surface only to one side of the film, thereby extending the persistence of the antifogging effect on that one side. A film consisting only of polymethacrylate or polyacrylate alone or a copolymer thereof is formed on one side of an antifogging film for agricultural chemicals selected from polyethylene and polyvinyl chloride mixed with an additive, and the antifogging film on the other side is A method of improving the anti-fog persistence of the film has been proposed to extend the persistence. Furthermore, Japanese Patent Publication No. 50-281117 discloses a monomer mixture with a specific composition, namely 70-90 parts by weight of methyl methacrylate, 5-30 parts by weight of methyl acrylate or ethyl acrylate, and 0.5-5 parts by weight of acrylic acid or methacrylic acid. An agricultural vinyl chloride film has been proposed in which a semi-rigid or flexible vinyl chloride film is coated with a resin coating film obtained by polymerizing a monomer mixture consisting of parts by weight on one or both sides of the film. As introduced above, agricultural anti-fog films or similar films are produced by providing a resin coating film on at least one side of a synthetic resin film containing an anti-fog agent to prevent migration of plasticizers and anti-fog agents to the coating side. In the conventional proposals regarding products, attention has been focused on means for preventing the above-mentioned migration by coating films made of acrylic or methacrylic resins, and many proposals as described above have been made. However, the various properties desired for anti-fog films for agriculture and horticulture, such as anti-fog properties, dustproof properties, crack resistance, anti-blocking properties, adhesion to the base film, and even heat sealability,
In practice, it has been extremely difficult to achieve both to a sufficiently satisfactory degree. Furthermore, there are technical issues arising from acrylic or methacrylic resin coatings, such as the difficulty of cloudy spots caused by raindrops appearing on the coating after rain, and poor anti-fog and dust-proof properties during high temperatures in summer. Overreach has been made regarding some of the issues. Furthermore, neither the intention nor the means to overcome these troubles and to improve the various properties described above have ever been proposed. The inventors of the present invention have found that they are able to solve the problems caused by acrylic or methacrylic resin coatings and the problems of combining the various properties desired in the above-mentioned anti-fog films for agriculture and horticulture, and furthermore, it is possible to exhibit anti-fog and dust-proof effects on both sides. We have been conducting research to provide an anti-fog and anti-dust film for agriculture and horticulture. As a result, in contrast to the conventional proposals that have focused exclusively on the formation of acrylic or methacrylic resin coatings, it has been found that coatings of cellulose ester resin compositions containing cellulose ester as a main component, It has been discovered that the above-mentioned problems can be solved all at once by providing an antifogging agent on at least one side of an olefin-based, ester-based, carbonate-based, or vinyl chloride-based synthetic resin film containing at least an antifogging agent. Therefore, an object of the present invention is to provide an anti-fog and anti-dust film for agriculture and horticulture which has a coating film of a cellulose ester resin composition and has excellent properties. Another object of the present invention is to provide a cellulose ester resin composition for coating an agricultural and horticultural film containing an antifogging agent, which is suitable for use in providing such a film. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The anti-fog and dust-proof film for agriculture and horticulture of the present invention has a coating film of a cellulose ester resin composition on at least one side of an olefin-based, ester-based, carbonate-based, or vinyl chloride-based synthetic resin film containing at least an anti-fog agent. . As described above, the cellulose ester resin composition contains about 50 to about 90% by weight, preferably about 90% by weight, based on the total weight of (i) to (iii), (i) (i) and (ii) below. from about 55 to about 80%, more preferably from about 60 to 80%, by weight cellulose ester; (ii) from about 10 to about 50%, preferably from about 20% by weight, based on the combined weight of (i) and (ii); - about 45% by weight, more preferably about 20 to about 40% by weight of a polymer or copolymer of an alkyl methacrylate and/or at least one alkyl methacrylate and an amount of an acrylic alkyl ester as a subcomponent, (iii) (i) 0 to about 5% by weight, based on the combined weight of and (ii)
This is a cellulose ester resin composition comprising an antifogging agent. As the cellulose ester (i) above, it is preferable to use _C1 to _C4 fatty acid esters of cellulose.
The ester may be in the form of a half-ester, monoester, diester or higher polyester, or may be in the form of a mixed ester of multiple types of fatty acids. Furthermore, it can be in the form of a mixture consisting of any combination of these esters. Specific examples of preferred cellulose esters include cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose tripropionate, cellulose acetate butyrate, cellulose tributyrate, cellulose propionate butyrate, and cellulose esters thereof. Mixtures consisting of any combination of these can be mentioned. Preferably cellulose acetate butyrate is utilized. Cellulose acetate butyrate has an acetyl group content of 6 to 30 wt% and a butyryl group content measured based on ASTM D-817.
Cellulose acetate butyrate having an acetyl group content of 54 to 17 wt%, preferably an acetyl group content of 6 to 25 wt% and a butyryl group content of 48 to 20 wt%, more preferably an acetyl group content of 10 to 15 wt% and a butyryl group content of 40 to 30 wt%. % of cellulose acetate butyrate. In addition, as the above (ii) methacrylate resin, polymers and copolymers of C ₁ -C ₁₈ alkyl esters of methacrylic acid, mixtures of at least two thereof, and/or C _{1 -C 18} alkyl esters of methacrylic acid are used. ₁₈
and at least one alkyl ester of acrylic acid in an amount copolymerizable with the alkyl ester of acrylic acid, an α-/β-unsaturated fatty acid, an epoxidized alkyl ester of acrylic acid, and another copolymer selected from the group consisting of styrenes. Examples include copolymers of monomers. Such other comonomers may be present in an amount on the order of about 0 to about 50% by weight, more preferably about 0 to about 40% by weight, based on the total weight of the alkyl ester or esters of methacrylic acid. It is preferable to use a moderate amount. Specific examples of the other comonomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-
Acrylic acid alkyl esters such as butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate; for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
α-/β-unsaturated fatty acids such as maleic acid; epoxidized alkyl esters of acrylic acid such as glycidyl acrylate and tetrahydrofurfuryl acrylate; styrenes such as styrene and vinyltoluene, and combinations of any plurality thereof. can be mentioned. Further, specific examples of the _C1 to _C18 alkyl ester monomer of methacrylic acid include methyl methacrylate, ethyl methacrylate, propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, and i-butyl. methacrylate, t-butyl methacrylate,
Examples include cyclohexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, methoxymethyl methacrylate, and butoxymethyl methacrylate. can. Further, as the antifogging agent (iii) above, a fatty acid sorbitan ester selected from the group consisting of sorbitan monoesters, diesters and sesquiesters of _C12 to _C22 fatty acids, more preferably _C16 to _C22 fatty acids. It is preferable to use them alone or in any combination. Specific examples of such fatty acid sorbitan esters include sorbitan laurate, sorbitan myriritate, sorbitan palmitate, sorbitan stearate, sorbitan isostearate, sorbitan behenate, sorbitan oleate, sorbitan hydroxystearate, and sorbitan palmitate. ethylene oxide adduct of tate,
Mention may be made of fatty acid sorbitan esters such as ethylene oxide adducts of sorbitan stearate. Furthermore, the base film used in the present invention,
That is, as the antifogging agent used in an olefin-based, ester-based, carbonate-based, or vinyl chloride-based synthetic resin film containing at least an antifogging agent, fatty acid sorbitan esters similar to the above-mentioned (iii) antifogging agent are preferably used. The antifogging agent used in the base film and the antifogging agent (iii) may be the same or different. Further, examples of the resin of the olefin base film include polyethylene, ethylene-vinyl acetate copolymer, polypropylene, etc.
Examples of the resin for the ester base film include polyethylene terephthalate, polybutylene terephthalate, etc. Examples of the resin for the carbonate base film include bisphenol A polycarbonate, and the vinyl chloride base film. - Examples of films include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer alone or any of these. Examples include combinations. These base film resins may optionally contain other resins compatible with the resin in accessory amounts, such as up to about 50% by weight, more preferably about 30% by weight, based on the weight of the base film resin. Other resins may be contained. Specific examples of such other resins include polymethyl acrylate, polybutyl acrylate, polydodecyl methacrylate, polystearyl methacrylate, polybutyl acrylate, poly2-ethylhexyl acrylate, methyl methacrylate-butyl acrylate copolymer, and methyl acrylate. Methacrylate-dodecyl acrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-2-ethylhexyl acrylate copolymer, ethylene-vinyl acetate copolymer, methyl methacrylate-butadiene-styrene copolymer ,
One or any combination of resins such as acrylonitrile-butadiene-styrene copolymer can be exemplified. (i) cellulose ester as exemplified above;
(ii) In a cellulose ester resin composition comprising a methacrylate resin and further an optional component (iii) an antifogging agent, if the amount of (i) cellulose ester is less than the above range, high temperatures may occur during summer. The dust resistance during storage deteriorates, and the blocking performance during storage deteriorates.
Further, defects such as increased cracking properties during tension occur. Furthermore, if the amount of cellulose ester (i) is too excessive beyond the above-mentioned range, the adhesion to the base film will be poor, resulting in the disadvantage of easy peeling. Therefore, in the present invention, the (i) cellulose ester should be used in the above amount range,
Particularly preferred is the use of about 70±5% by weight based on the total weight of (i) and (ii). Furthermore, (ii) the amount of methacrylate resin exceeds the above amount range;
(i) If the amount exceeds cellulose ester, the dustproof property at high temperatures in summer will decrease, the blocking property will deteriorate, and the resistance to unwinding will increase. In addition, many serious troubles such as cracks becoming extremely severe occur, and the improvements made by the coating film of the cellulose ester resin composition are largely lost. Also, (ii)
If the amount of the methacrylate resin is too small and is less than the above range based on the total weight of (i) and (ii), it is unfavorable in terms of adhesion to the base film. Therefore, in the present invention, (ii) the methacrylate resin should be used in the above amount range of 50% by weight or less, in particular about 35% by weight based on the total weight of (i) and (ii). It is suitable for use in secondary amounts up to. Still further, the cellulose ester resin composition used in the present invention can contain up to about 5% by weight of (iii) an antifog agent, based on the combined weight of (i) and (ii). Applicable
(iii) If the amount of antifogging agent is too excessive beyond the above upper limit,
A bleed-out phenomenon occurs, reducing transparency and blocking properties. It is also undesirable because the dust resistance deteriorates initially, but it is about 5.
When utilized in amounts up to % by weight, it is possible to impart double-sided anti-fog effects to the anti-fog and dust-proof films of the present invention without adversely affecting the improved effects of the films, often giving favorable results. Furthermore, in the present invention, the cellulose ester resin composition described above contains, in addition to the above (i) cellulose ester, (ii) methacrylate resin, and (iii) antifogging agent, (ii)' 0 to about 20% by weight of vinyl chloride synthetic resin, based on the total weight of (i) and (ii); and (v) 0 to about 10% by weight, based on the total weight of (i) and (ii).
may contain a plasticizer. In addition to the polyvinyl chloride resin, the above (ii)′ vinyl chloride synthetic resin is preferably about 80% by weight, more preferably 60% by weight based on the weight of the copolymer.
Examples include copolymers of vinyl chloride and at least one of the comonomers copolymerizable with vinyl chloride. Specific examples of comonomers that can be copolymerized with vinyl chloride include vinyl acetate, vinylidene chloride, ethylene, propylene, acrylonitrile, and the like. Further, as the plasticizer (iv) above, preferably a polyester plasticizer can be used, and examples of such plasticizers include polypropylene adipate, polypropylene sebacate, polypropylene azelate, polyethylene adipate, polyethylene sebacate, polyethylene Examples include phthalates. The inclusion of plasticizers also serves to (iii) aid in the migration of the antifog agent to the surface of the coating. The amount of the vinyl chloride synthetic resin used in (ii)′ above is (i)
If the amount exceeds about 20% by weight based on the total weight of cellulose ester and (ii) methacrylate resin, compatibility tends to decrease and transparency tends to worsen, and also This is unfavorable in terms of reduced dust resistance. and (iv) the amount of plasticizer used exceeds about 10% by weight based on the total weight of (i) cellulose ester and (ii) methacrylate resin;
If it is in excess, it is undesirable as it tends to reduce the dustproof property at high temperatures in summer and also tends to worsen the blocking property. Therefore, in the present invention, when (ii)' vinyl chloride synthetic resin and (iv) plasticizer are used, they are preferably used within the above-mentioned amount ranges. The use of (ii)′ and (iv) has the advantage of improving adhesion, improving sealing performance, and improving flexibility at low temperatures, and also improves water repellency on the film surface after rain. It often produces favorable results in terms of good light transmittance because it suppresses the occurrence of cloudy spots and reduces dust adhesion. When producing an anti-fog and dust-proof film for agriculture and horticulture having a coating film of the cellulose ester resin composition of the present invention, an olefin-based, ester-based, carbonate-based or vinyl chloride-based resin as exemplified above containing at least an anti-fog agent is used. It can be easily manufactured by applying a coating composition consisting of a solvent solution of a cellulose ester resin composition to at least one side of a base film and drying the coating composition. The application means itself can be selected appropriately, and application means such as spray coating, roll coating, gravure coating, screen printing, and flexographic printing can be used. Appropriate means can be selected for drying, such as hot air drying, infrared drying, and far infrared drying. During coating, in order to further improve the heat sealability of both edges in the width direction of the film, the base film may be left uncoated without coating only those parts. Solvents used to form such coating solvent solution compositions include toluene, methyl acetate, ethyl acetate, methyl ethyl ketone, acetone, methyl butyl ketone, methanol, ethanol, isopropanol, tetrahydrofuran, methyl cellosolve, dimethyl formamide, and the like. can be exemplified. Furthermore, in the present invention, the base film made of an olefin-based, ester-based, carbonate-based, or vinyl chloride-based synthetic resin film may contain other additives, such as diethyl phthalate, dibutyl phthalate, di-n-octyl phthalate, di-2 - Phthalic acid esters such as ethylhexyl phthalate; e.g., sebacic acid esters such as di-2-ethylhexyl sebacate, dibutyl sebacate; e.g., di-2-ethylhexyl azelate, di-isooctyl azelate, dibutyl sebacate azelaic acid esters such as tri-(2-ethylhexyl);
Trimellitic acid esters such as trimellitate, tri-isodecyl trimellitate; adipic acid esters such as di(2-ethylhexyl) adipate, diisodecyl adipate, dibutyl adipate; tricresyl phosphate,
Phosphate esters such as trixylenyl phosphate; epoxidized fatty acid esters such as epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil; e.g. sebacic acid, adipic acid, azelaic acid, phthalic acid Plasticizers such as polyesters and the like may be included. Furthermore, waxes such as polyethylene wax and liquid paraffin; fatty acids such as stearic acid, oleic acid, and palmitic acid; fatty acid amides such as stearic acid amide, oleic acid amide, and palmitic acid amide; such as butyl stearate; , lubricants such as fatty acid esters such as methyl hydroxystearate. Furthermore, organotin stabilizers such as dibutyltin dilaurate, dibutyltin maleate ester, dioctyltin mercaptide; such as calcium stearate, barium stearate, zinc stearate, cadmium stearate, calcium laurate, barium ricinoleate, olein; Stabilizers such as metal soap stabilizers such as calcium oxide and zinc octoate can be included. Also, for example, t-butylhydroxytoluene, 2,2'-methylenebis(6
-t-butyl-4-ethylphenol), dilaurylthiodipropionate and stabilizing aids such as triphenylphosphite, dioctylphosphite, tris(phenylphenyl)phosphite, trilauryltrithiophosphite. In addition, coloring agents such as phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc white, permanent red, carbon black, and quinacridone can be included. In the present invention, the base film and/or the cellulose ester resin composition may contain an ultraviolet absorber capable of preventing the transmission of ultraviolet light including near ultraviolet light of 380 nm or less. Examples of such ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-
5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-
(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-
2'-hydroxyphenyl-5- such as 5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole;
Chlorobenzotriazole UV absorbers, such as 2-(2'-hydroxy-3',5'-di-tertbutylphenyl)benzotriazole, 2-(2'-
2'-hydroxyphenylbenzotriazole UV absorbers such as hydroxy-5'-methylphenyl)benzotriazole, such as 2,2'-dihydroxy-4-methoxybenzophenone, 2,
2,2'-dihydroxybenzophenone ultraviolet absorbers such as 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, e.g. 2-hydroxybenzophenone UV absorbers such as hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; cyano such as 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate; Examples include acrylate-based ultraviolet absorbers, such as salicylic acid ester-based ultraviolet absorbers such as phenyl salicylate. Among these ultraviolet absorbers, benzophenone-based and benzotriazole-based ones are preferred, and among the benzophenone-based ones, 2,3'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone and 2,2',4,4'-tetrahydroxybenzophenone; 2-
(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5,6-dichlorobenzotriazole, 2-(2'-hydroxy-5'-tertiary butylphenyl) benzotriazole, 2-(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)
Benzotriazole, 2-(2'-hydroxy-
3',5'-di-tert-butylphenyl)-5-chloro-
Benzotriazole and 2-(2'-hydroxy-
5′-phenylphenyl)-5-chlorobenzotriazole, 2(2′-hydroxy-3′,5′-dithyabutylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-5′- octoxyphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-
(2'-Hydroxy-3'-tertiary butyl-5'-methylphenyl)-5,6 dichlorobenzotriazole and the like are effective. Particularly suitable UV absorbers have the formula or In the formula, R ₁ and R ₂ are the same or different,
Each represents a lower alkyl group or an aryl group (especially a phenyl group), and R ₁ is preferably
A branched lower alkyl group or phenyl group of C ₅ or less, R ₃ represents an alkyl group of C ₆ or more, especially C ₈ to _{C 10} , and X is a hydrogen atom or a halogen atom, especially a chlorine atom. It is a benzotriazole derivative represented by The amount of the ultraviolet absorber mentioned above can vary widely depending on the type of ultraviolet absorber, the type of synthetic resin used, the thickness of the film or plate, the shape of the molded product, etc. Generally, the range of 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 0.1 to 2.5 parts by weight per 100 parts by weight of the synthetic resin for base film or cellulose ester resin composition is suitable. Hereinafter, several embodiments of the anti-fog and dust-proof film for agriculture and horticulture of the present invention will be explained in more detail with reference to comparative examples and examples. In addition, in the following examples, the test method and evaluation are as follows. (1) Anti-fog and dustproof test: - (Part 1) A test house with a wooden frame with a width of approximately 3 m, a depth of approximately 4 m, a ridge height of approximately 1.5 m, and a roof slope of approximately 30 degrees is used. The roof was constructed with multiple wooden frames (spans) each having a length of 1 m in the ridge direction and 1.2 m in the roof slope direction. Measurements will be made at A test film is spread over the entire surface of the house except the bottom, and an accessible test house is constructed outdoors, and an anti-fog and dust-proof test is conducted under natural outdoor conditions. There is a temperature controller inside the house.
A hot water tank maintained at 35℃ was installed, the temperature inside the house was always maintained at 100%, and after a specified period of time, the amount of solar radiation was actually measured using two Ishikawa visible-ray pyranometers.
One device measures the amount of solar radiation outside the house, and the other device measures the amount of solar radiation inside the house at a position 20 cm directly below the center of the test film stretched across the center span. It is expressed as a percentage of the actual value inside the house compared to the actual value outside the house. The larger the % value, the better the anti-fog and dust-proof properties. (Part 2) Anti-fog and dustproof test at high temperatures Attach a 60 x 60 m/m test film to a glass plate with the coating side up using double-sided adhesive tape.
Clean the coating surface with powdered soap (synthetic detergent for washing). Place the glass plate in an electric incubator (Kiya Seisakusho Model A-2) at 50°C to dry it, and then cool it to room temperature. Next, approximately 35 g/m ² of talc (Wako Pure Chemical Reagent Grade 1) is sprinkled on the coating surface of the test film. This was placed in an electric incubator at 50°C for 3 days, then taken out and allowed to cool to room temperature. Next, tilt the glass plate at an angle of about 30 degrees, and sprinkle 20/m ³ of water over about 1 minute from a height of about 300 m/m. Thereafter, the film was placed in an electric incubator at 50° C. for about 1 hour to dry the surface of the film, and then cooled to room temperature. Next, cut the film to a size of 20 x 40 m/m, measure the diffuse transmittance and total transmittance with an integrating sphere turbidity meter (Japan Seimitsu Optics, model: SEP-T), and calculate the haze (degrees) using the following formula. . Haze (%) = Diffuse transmittance (%) / Total transmittance (%) ×
100 The smaller the haze value, the better the anti-fog and dust-proof properties. A similar test was conducted at 60°C and the results were evaluated. (2) Cracking resistance test: - Tensilon (manufactured by Toyo Baldwin, model UTM-1-5000B) test film of 80 x 80 m/m
, set the distance between the gauge lines to 40m/m, grab it, and set it to 500mm/mi.
After stretching to 100% elongation (40→80m/m) at n,
Return at the same speed. Repeat this operation three times. This film is cut into a size of 20 x 40 m/m and the haze (%) is determined in the same manner as in the anti-fog and dust-proof test (Part 2). The smaller the haze value, the better the crack resistance. (3) Blocking resistance test: - 30× on a glass test tube (15ψ×150m/m)
A 300 m/m test film is wound up with the coating on the inside while applying a load of 750 g to one end. Transfer the rolled material to a beaker, place the beaker in a desiccator filled with water at the bottom, and incubate at 100% humidity in an electric incubator at 50°C.
After keeping it for a week, take it out, dry it in an electric incubator at 50°C, and then cool it to room temperature. Attach sellotape to the end of the roll and attach the weight to the sellotape. Gently rotate the test tube in the direction in which the film will be rewound. If the weight load does not cause unwinding, replace the test tube with a weight with a heavier load and repeat the test. Measure the load (g/30mm). The smaller the unwinding load, the better the blocking resistance. (4) Adhesion test with base film: - After subjecting the test film to three stretching and restoring operations in the same manner as the crack resistance test above, the film was placed in an electric incubator at 50℃ and humidity. The sample was kept at 100% for one week, then taken out from the incubator, dried at 50°C, and cooled to room temperature. Apply Cellotape (manufactured by Sekisui, 18m/m width) to a length of 50m/m on the coating side of this film, press it firmly with your fingers, then peel it off vigorously to check the degree to which the coating surface peels off from the base material. View. 〇: No peeling at all △: Less than 20% peeling ×: 20% or more to 50% peeling × ×: 50% or more peeling (5) Heat sealability test: - Output using a high frequency sewing machine made by Takano Electric. At dial scale 55 and speed scale 2 (file feed speed 3 m/min), the coated and uncoated surfaces were overlapped and sealed, and this sample was
It was cut into cm width x 10 cm length, and the stress (Kg/cm) required for breakage or peeling was determined using a tensile tester. (6) Curling test: - Grasp one end of the test film cut to 80 x 80 m/m with your fingers and lift it to check the degree of curl. 〇: Not curled at all △: Slightly curled ×: Significantly curled (7) Tack test immediately after production: - Edge of base film fixed to glass plate in advance with coating liquid adjusted to 10% solids concentration After washing, immediately coat with a wire bar (manufactured by Kodaira Seisakusho, wire diameter 0.15 m/m) and dry in a hot air dryer (manufactured by Tabai, model HPS-11) at 140℃ for 4 minutes to evaporate the solvent. After cooling to room temperature, check the adhesion of the coated surface with your finger. Furthermore, the degree of peeling is observed after the coated surfaces are pressed together with fingers. 〇: No tackiness at all △: Slight tackiness ×: Significant tackiness (8) Transparency test: - Test film (base film thickness 150μ:
Cut the coating film (thickness 3μ) to 20 x 40m/m, measure the diffused transmittance and total transmittance with an integrating sphere turbidity meter, and calculate the haze (%)〇: Haze 5% or less△: Haze 6-10 % ×: Described as haze 11% or more. In addition, in the following examples and comparative examples, the abbreviations are as follows. Base film: - Part by weight Polyvinyl chloride resin (degree of polymerization 1300) 100 Dioctyl phthalate (plasticizer) 40 Tricresyl phosphate (plasticizer) 5 Epoxidized soybean oil (plasticizer) 5 Cadmium stearate (stabilizer) 1 Barium stearate (stabilizer) 0.2 Sorbitan monostearate (anti-fog agent) 1.3 Sorbitan monopalmitate (anti-fog agent) 0.7 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (ultraviolet absorber) 0.8 and calendered at 170℃ to a thickness of 150℃.
Use micron base film. Base film B: - Instead of the ultraviolet absorber in the above base film A, 2-(2'-hydroxy-3',5'-di-
A base film having a thickness of 150 microns was made from the same composition as above, except that 0.7 parts by weight of tertbutylphenyl)-5-chlorobenzotriazole was used. CAB No. 1: - According to ASTM D-817 (the same applies hereafter) acetic acid group content 13% by weight, butyryl group content 37% by weight, ASTM
Cellulose acetate butyrate with a falling ball viscosity of 0.5 seconds (manufactured by Eastman Kodak, EAB381-05) by D-1343 (hereinafter the same). CAB No. 2: - Cellulose acetate butyrate (manufactured by Eastman Kodak, EAB381-20) with an acetic acid group content of 13% by weight, a butyryl group content of 37% by weight, and a falling ball viscosity. CAB No. 3: - Cellulose acetate butyrate with an acetate group content of 3% by weight, a butyryl group content of 54%, and a falling ball viscosity of 0.2 seconds (manufactured by Eastman Kodak, EAB551-
02). MMA-DMA copolymer: - Methyl methacrylate-dodecyl methacrylate copolymer, MMA/DMA ratio 82wt%/
18wt%, molecular weight approximately 80,000. MMA-BA copolymer: - Methyl methacrylate-butyl acrylate copolymer, MMA/BA ratio 94wt%/6wt%, molecular weight approximately 80,000. MMA-EMA copolymer (1): - Methyl methacrylate-ethyl methacrylate copolymer, MMA/EMA ratio 40wt%/60wt
%, molecular weight approximately 200,000. MMA-EMA copolymer (2): - Methyl methacrylate-ethyl methacrylate copolymer, MMA/EMA ratio 88wt%/12wt
%, molecular weight approximately 100,000. MMA polymer: - Polymer of methyl methacrylate, molecular weight approx. 10
Ten thousand. MMA-BMA-St copolymer: - Methyl methacrylate-butyl methacrylate styrene copolymer, MMA/BMA/St ratio
60wt%/20wt%/20wt%, molecular weight approximately 80,000. MMA-EMA-AA copolymer: - Methyl methacrylate-ethyl methacrylate-acrylic acid copolymer, MMA/EMA/AA
The ratio is 85wt%/12wt%/3wt% and the molecular weight is approximately 120,000. PVC: - Polyvinyl chloride (degree of polymerization 450) Polyester plasticizer: - Polypropylene adipate (molecular weight 2000) Examples 1 to 13 and Comparative Examples 1 to 11 On the base film shown in Table 1 below, A coating film of the coating composition shown was formed. The coating film is prepared by gradually adding and dissolving resins and other additives in a mixed solvent of methyl ethyl ketone/toluene (weight ratio 1:1) at the ratios shown in the ratio (wt%) column of Table 1.
A wire bar (0.15m/m wire diameter) was coated with the coating liquid adjusted to 10%, and then heated in a hot air dryer.
It was formed by drying at the drying temperature shown in Table 1 and for 4 minutes. The results of testing the performance of the obtained anti-fog and anti-dust film are shown in Tables 1 to 3 below. In addition, when adjusting the test film in the anti-fog and dust-proof test (Part 1), the roll surface length is 1200 mm.
Using a three-roll reverse roll coater with a width of m/m, the coating was adjusted so that the thickness of the coating after drying was 2 microns. Table 1 also shows the results of Comparative Examples 1 to 11, which did not satisfy the essential requirements of the present invention, and a comparative example using only the base film.

【table】

【table】

[Table] Table 3 Heat sealability test example number Seal strength (Kg/cm) Example 1 0.3 Example 6 0.6 Example 7 0.7 Comparison* 0.3 *MMA-BMA-2HEMA-AA copolymer (weight ratio 45: 35:18:2) Isopropyl alcohol solution

Claims (1)

[Scope of Claims] 1. The following (i) to (iii), (i) (i) is applied to at least one side of an olefin-based, ester-based, carbonate-based, or vinyl chloride-based resin film containing at least an antifogging agent. Approximately 50-90% by weight, based on the combined weight of and (ii)
(ii) from about 10 to about 50% by weight, based on the combined weight of (i) and (ii), of at least a polymer or copolymer of an alkyl methacrylate ester and/or an alkyl methacrylate ester; A meta-polymer consisting of a copolymer of one type and a subcomponent amount of an acrylic acid alkyl ester, an α-/β-unsaturated fatty acid, an acrylic acid epoxidized alkyl ester, and another comonomer selected from the group consisting of styrenes. acrylate resin, and (iii) 0 to about 5% by weight, based on the total weight of (i) and (ii).
1. An anti-fog and dust-proof film for agriculture and horticulture, comprising a coating film of a cellulose ester resin composition containing an anti-fog agent. 2. The amount of the cellulose ester is about 55 to about 80% by weight based on the total weight of (i) and (ii), and the amount of the methacrylate resin is less than the total weight of (i) and (ii). from about 20 to about 45% by weight based on
Film mentioned in section. 3 The cellulose ester is C ₁ of cellulose
~ _C4 fatty acid ester Claim 1
Film mentioned in section. 4. The film according to claim 3, wherein the cellulose fatty acid ester is cellulose acetate butyrate. 5. The film according to claim ₁ , wherein the methacrylate resin is a polymer or copolymer of C1 to _C18 alkyl esters of methacrylic acid, or a mixture of at least two thereof. 6 The antifogging agent contained in the synthetic resin film and the antifogging agent contained in the synthetic resin film.
The antifogging agents in (iii) are the same or different and have C ₁₂ to _{C 22}
The film according to claim 1, which is a sorbitan monoester and/or diester and/or sesquiester of a fatty acid. 7. Claim 1, wherein the cellulose ester resin composition further contains up to about 10% by weight of (iv) a plasticizer, based on the total weight of (i) and (ii). Film mentioned in section. 8. The film according to claim 1, wherein the plasticizer is a polyester plasticizer. 9. The cellulose ester resin composition contains up to about 20% by weight of (ii)' based on the total weight of (i) and (ii).
2. The film according to claim 1, further comprising a vinyl chloride synthetic resin. 10 (i) to (iv) below; (i) about 50 to about 90% by weight of cellulose ester, based on the total weight of (i) and (ii); (ii) the sum of (i) and (ii); Based on the weight, from about 10 to about 50% by weight of a polymer or copolymer of an alkyl methacrylate and/or at least one alkyl methacrylate and an amount of an acrylic alkyl ester, α-/β, as a subsidiary component. - methacrylate resins consisting of copolymers with unsaturated fatty acids, epoxidized alkyl esters of acrylic acid, and other comonomers selected from the group consisting of styrenes, (ii)' (i) and (ii) (iii) 0 to about 5% by weight, based on the total weight of (i) and (ii); (iii) 0 to about 5% by weight, based on the total weight of (i) and (ii);
and (iv) 0 to about 10% by weight, based on the combined weight of (i) and (ii).
A composition for coating cellulose ester-based agricultural and horticultural films containing an antifogging agent, comprising a solvent solution of a cellulose ester-based resin composition containing a plasticizer.