JP2015195776A - agricultural film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural film which can provide a light quality balance ideal for plants.SOLUTION: An agricultural film comprises an isoindolinone pigment.

Description

  The present invention relates to an agricultural film having an adjusted R / B ratio, and more particularly to an agricultural polyolefin resin film having an adjusted R / B ratio containing a specific pigment. The present invention also relates to an agricultural film having an adjusted R / B ratio and R / G ratio including a specific pigment combination.

  In recent years, the domestic agricultural population has been declining with the aging of the population, and there is a need for a mechanism that enables new leaders of agricultural production to obtain stable income. From the viewpoint of food security, there is an urgent need to improve the agricultural production method, increase the yield per unit area, and build a mechanism that enables stable and efficient agricultural production.

  Under such circumstances, a so-called fully-controlled plant factory, which is cultivating crops by irradiating artificial light sources in buildings, has attracted attention. In a fully controlled plant factory, the yield per unit area is increased, so that it becomes a multi-stage cultivation method, which makes it difficult to grow tall crops and enormous initial investment. Due to such constraints, it has been utilized mainly for leaf vegetable cultivation with a short cultivation period and high turnover. In this cultivation form, crops can be cultivated in a very short period of time by environmental management such as optimum temperature and humidity, light environment, nutrient solution, etc., but the cultivated crops are very limited and cannot be used for fruits and vegetables. In addition, once a pest occurs, there is a problem that enormous effort and cost are required for its control. For this reason, it was necessary to prepare expensive equipment such as an air shower so that the cause of the occurrence of pests was not brought into a sterile facility.

  On the other hand, the cultivation form by institutional horticulture using a resin film or the like has evolved according to the cultivation form of various crops in order to stably obtain agricultural income as compared with open field cultivation. To increase the yield per unit area, it is effective to increase the size of agricultural houses from the viewpoint of work efficiency and cultivation environment management. It has become necessary to work manually. However, the number of farmers is decreasing year by year and aging is progressing, and it is not easy to secure manpower for the annual expansion work. In view of such a situation, as a film to be spread in a house used in a solar-powered plant factory, a film that is easy to extend and has a long use period until re-covering as much as possible, in other words, has a long life of 2 years or more. In addition to the development of high-performance agricultural covering materials that can maintain the initial performance over a long period of time, it is required that lining materials that are used internally, for example, can be used for a long period of time due to the deterioration protection of internal materials. It is coming.

  In addition, attempts have been made to carry out pesticide-reducing cultivation by imparting pest control of fungi and fungi and pest control to the environment in the house. Gray mold disease and mycorrhizal disease are typical diseases occurring in the house, causing damage to the stalks, leaves, flowers, fruits, etc. of various crops. Onsitsuna lice, southern blue thrips, citrus white thrips are typical pests of crops widely cultivated in the house such as tomatoes, cucumbers, melons, strawberries, and flower buds. In addition, it causes a great deal of damage such as mediating viral diseases such as soot fungus parasitism on excrement and tomato yellow wilt virus disease. In view of the recent safety requirements for agricultural crops, specific methods for controlling these diseases and pests are desired for cultivation with reduced pesticides. Countermeasures for these diseases and pests have become a very important issue in greenhouse horticulture.

  As a method of increasing the yield per unit area while reducing the quality risk, a method of supplementing the amount of light necessary for photosynthesis by supplementary light has been attracting attention during cloudy weather. For example, incandescent bulbs, fluorescent lamps, high-pressure sodium lamps, halogen lamps, light-emitting diodes (LEDs), and the like may be used as lighting devices to compensate for the lack of sunshine during cultivation. Compared with, the illuminance is often low, and in order to obtain the illuminance, a large amount of energy is required, and there is a demerit that the economic efficiency deteriorates. Furthermore, since the light from the light source is locally irradiated, it is difficult to exert the irradiation effect on the plant body over the entire cultivation area. On the other hand, if the number of irradiation devices is increased to irradiate the entire cultivated crop, it becomes inefficient due to the influence of the devices themselves, which is a problem.

  As means for solving such problems of electric energy cost and local irradiation, for example, a wavelength conversion film as disclosed in JP-A-7-123870 (Patent Document 1) is cited. These wavelength conversion films are intended to improve cultivation by using fluorescent materials to convert light with high energy at short wavelengths into light that is absorbed by the photoreceptors at long wavelengths, especially during photosynthesis. is there. In particular, there are many studies for increasing red light of 600 to 700 nm, and the amount of light accumulated by wavelength conversion is extremely small compared to the case of using an auxiliary light device. Therefore, the magnitude of the use effect when viewed from the whole plant depends on how high and long-lasting the wavelength conversion efficiency is. However, even if the wavelength conversion film using the prior art is commercialized, the wavelength conversion effect is not sufficient, and the wavelength conversion effect disappears in about 4 months, and the effect does not continue for a high film unit price. Things were a problem. In addition, a similar wavelength conversion material has been proposed in Japanese Patent Application Laid-Open No. 2007-135583 (Patent Document 2). However, in practice, the perylene wavelength conversion material used in the examples has low effect sustainability. In addition, although it is compatible with a polyester-based resin, it is not compatible with a polyolefin-based resin, and there is a practical problem such that a wide film cannot be formed.

  The present inventors have found that a specific fluorescent material can effectively supplement light over a long period of time, and furthermore, surprisingly, it has been found that this fluorescent material has an antifogging agent and an antagonistic action. did. As a result of further studies, a means capable of avoiding this antagonism could be found (Patent Document 3).

  Such a wavelength conversion film absorbs light having a short wavelength and high energy (for example, blue light) and emits long wavelength light (600 to 700 nm red light), thereby increasing the wavelength effective for plants. However, further verification is required for the risks of blue light dimming. In the wavelength conversion film, a specific fluorescent pigment is used, but such a fluorescent pigment is generally difficult to obtain.

JP 7-123870 A JP 2007-135583 A JP 2011-115073 A

  An object of the present invention is to provide an agricultural film capable of providing an ideal light quality balance for plants.

The present inventors have adjusted the R / B ratio by absorbing light in a predetermined wavelength range without using a means of wavelength conversion that absorbs short wavelength light and emits long wavelength light. The inventors considered that it would be possible to provide an ideal light quality balance for plants, and intensively studied. As a result, they found that the RB balance can be adjusted by using a specific pigment, and completed the present invention.
Furthermore, the present inventors have found that by using a specific combination of pigments, it is possible to adjust the R / G ratio in addition to the R / B ratio, and to complete the present invention. It came.
In other words, the use of the wavelength conversion film provides a strong light environment of red light and improves the cultivatability as described in Patent Document 3, but the present invention uses a highly durable pigment. Thus, it is a technical feature that a strong light environment of red light similar to that when the wavelength conversion film is used can be obtained.

That is, the present invention
[1] An agricultural film containing an isoindolinone pigment.
[2] The agricultural film according to [1], further comprising dioxazine violet.
[3] An agricultural polyolefin resin film comprising a polyolefin resin composition containing an isoindolinone pigment.
[4] The agricultural polyolefin resin film according to [3], wherein the polyolefin resin composition contains dioxazine violet.
It exists in

According to one embodiment of the present invention, an agricultural film having an adjusted R / B ratio can be provided.
Moreover, according to one embodiment of the present invention, an agricultural film having an adjusted R / G ratio in addition to an R / B ratio can be provided.
The agricultural film of the present invention can provide an ideal light quality balance for plants.

Total light transmittance measurement data of Examples 1 to 3 and Comparative Example 4 Total light transmittance measurement data of Examples 4 to 6 and Comparative Example 4 Total light transmittance measurement data of Examples 7 to 9 and Comparative Example 4 Total light transmittance measurement data of Comparative Examples 1 to 4 Spectral radiometer measurement data of Examples 1 to 3 and Comparative Example 3 Spectral radiometer measurement data of Examples 4 to 6 and Comparative Example 3 Spectral radiometer measurement data of Examples 7 to 9 and Comparative Example 3 Spectral radiometer measurement data of Comparative Examples 1 to 4 Comparison of RB ratio, RG ratio and visible light transmittance of each film Initial total light transmittance of Example 10 and Comparative Example 5 Total light transmittance after the fastness test of Example 10 and Comparative Example 5

  Hereinafter, the present invention will be described in detail.

  As an agricultural film material (base resin) that can be used in the present invention, it is generally a film forming ability that can be melt-molded at about 150 to 250 ° C. and is generally used for an agricultural covering material. Any one can be used, but polyvinyl chloride resins such as polyvinyl chloride, polyolefin resins and the like are preferable.

  In the present invention, the vinyl chloride resin refers to a copolymer in which vinyl chloride is the main component in addition to polyvinyl chloride. Examples of the monomer compound that can be copolymerized 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 the conventionally known production methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

  In the present invention, as the vinyl chloride resin, those having an average polymerization degree of 1000 or more and 2500 or less, preferably 1100 or more and 2000 or less can be used. May be. As this mixing method, a method of mixing two kinds of resins at the time of film formation processing is generally used, but two kinds of resins having apparently different average degrees of polymerization can be obtained by controlling the polymerization conditions at the time of polymerization of vinyl chloride resin. It may be a mixed method.

  In order to impart flexibility to the vinyl chloride resin film, 30 to 60 parts by weight, preferably 40 to 55 parts by weight of a plasticizer is blended with respect to 100 parts by weight of the resin. If it is less than 30 parts by weight, sufficient low-temperature physical properties cannot be obtained because of low flexibility at low temperatures. On the other hand, if it exceeds 60 parts by weight, the handleability (stickiness, etc.) at room temperature deteriorates and the workability at the time of film formation decreases, which is not preferable.

  Examples of the plasticizer that can be used include phthalic acid derivatives such as di-n-octyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate, and diisodecyl phthalate; isophthalic acid derivatives such as dioctyl phthalate; di-n-butyl adipate Adipic acid derivatives such as dioctyl adipate; maleic acid derivatives such as di-n-butyl malate; citric acid derivatives such as tri-n-butyl citrate; itaconic acid derivatives such as monobutyl itaconate; oleic acid such as butyl oleate Derivatives; ricinoleic acid derivatives such as glycerin monoricinoleate; epoxidized large oil, epoxy resin plasticizer, and the like. Moreover, in order to give a softness | flexibility to a resin film, it is not restricted to the above-mentioned plasticizer, For example, a thermoplastic polyurethane resin, a polyvinyl acetate, etc. can also be used.

  Moreover, what blended polyvinyl chloride and chlorinated polyethylene can also be used as a vinyl chloride resin. As the chlorinated polyethylene, the raw material polyethylene is ethylene homopolymerization, or ethylene and 30% by weight or less (preferably 20% by weight or less) and 12 or less carbon atoms (preferably 3 to 9). Those obtained by copolymerizing these α-olefins are preferred.

  Specific examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and the like. As polyolefin used as a raw material, what homopolymerized ethylene especially is preferable. As the chlorinated polyethylene, a method in which polyethylene powder or particles are chlorinated in an aqueous suspension or polyethylene dissolved in an organic solvent is chlorinated.

  The amount of chlorinated polyethylene added to the vinyl chloride resin is usually 0.5 to 20 parts by weight, preferably 0.5 to 10 parts by weight. The melt index of chlorinated polyethylene can be appropriately selected within the range of 0.5 to 150 g / 10 minutes.

  Examples of polyolefin resins include α-olefin homopolymers, copolymers of different monomers mainly containing α-olefins, polyunsaturated compounds such as α-olefins and conjugated dienes or nonconjugated dienes, Examples include copolymers with acrylic acid, methacrylic acid, vinyl acetate, and the like, such as high density, low density or linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene. Examples include -4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Among these, low density polyethylene having a density of 0.910 to 0.935, an ethylene-α-olefin copolymer, and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less have transparency and weather resistance. It is preferable as an agricultural film from the viewpoint of properties and price. In the present invention, an ethylene-α-olefin copolymer resin obtained by copolymerization with a metallocene catalyst can be used as at least one component of the polyolefin resin.

  This is usually referred to as metallocene polyethylene, and is a copolymer of ethylene and an α-olefin such as butene-1, hexene-1, 4-methylpentene-1, octene. (Method A) (JP 58-19309, JP 59-95292, JP 60-35005, etc.) and (B) (JP 6-9724, JP 6-136195, No. 6-136196).

  A polyolefin resin polymerized by using a metallocene compound, that is, a metallocene polyethylene, is not limited to the above methods (A) and (B) in that good initial transparency and transparency persistence of the film can be obtained. Can be used.

  Polyethylene resins including these metallocene polyethylenes are classified based on temperature rising elution fractionation (TREF), MFR, density, molecular weight distribution, and other various physical properties. Measurement of elution curve by temperature rising elution fractionation (TREF) is described in “Journal of Applied Polymer Science. Vol 126, 4, 217-4, 231 (1981)”, “Polymer Discussion 0 Proceedings 2P1C”. This is carried out based on the principle described in the literature such as “Showa 63”.

The ethylene-α-olefin copolymer used as at least one component of the polyolefin resin of the present invention has an MFR measured by JIS-K7210 of 0.01 to 10 g / 10 min, preferably 0.1 to 5 g / A value of 10 minutes is shown. If the MFR is larger than this range, the film meanders during molding and is not stable. On the other hand, if the MFR is too smaller than this range, the resin pressure at the time of molding increases and a load is applied to the molding machine. Therefore, the increase in pressure must be suppressed by reducing the production amount, which is not practical. The ethylene-α-olefin copolymer used as at least one component of the polyolefin-based resin of the present invention has a density measured by JIS-K7112 of 0.880 to 0.930 g / cm ³ , preferably 0.8. A value of 880 to 0.920 g / cm ³ is shown. When the density is larger than this range, the transparency is deteriorated. On the other hand, if the density is smaller than this range, blocking occurs due to stickiness of the film surface, resulting in poor practicality. The ethylene-α-olefin copolymer used as at least one component of the polyolefin resin of the present invention has a molecular weight distribution (weight average molecular weight / number average molecular weight) determined by gel permeation chromatography (GPC). The value is 1.5 to 3.5, preferably 1.5 to 3.0. When the molecular weight distribution is larger than this range, the mechanical strength is lowered, which is not preferable. If the molecular weight distribution is smaller than this range, the film meanders during molding and is not stable.

  As the ethylene-vinyl acetate copolymer resin, those having a vinyl acetate content in the range of usually 10 to 25% by weight and preferably in the range of 12 to 20% by weight can be used. If the vinyl acetate content is less than this range, the resulting film will be hard and will tend to wrinkle and sag when stretched in a house, which will have a negative effect on anti-fogging properties. If it is larger than the range, the melting point of the resin is low, so that the film loosens at high temperatures in summer during house extension, and is easily broken by wind and flapping with the house structure.

One embodiment of the present invention is an agricultural film comprising isoindolinone pigment. By including isoindoline, it is possible to adjust the R / B ratio so as to absorb blue light and transmit red light. In this specification, the R / B ratio of blue light and red light means the ratio of the amount of transmitted light at 660 nm to the amount of transmitted light at 460 nm.
In the agricultural film of the present invention, the R / B ratio is preferably 1.5 or more, and more preferably 1.7 or more.

  In the agricultural film of the present invention, the content of isoindolinone pigment is 0.01 to 3.0% by weight, preferably 0.05 to 2.0% by weight, based on the total weight of the agricultural film. Preferably it is 0.1 to 1.5 weight%. By setting the content of the isoindolinone pigment within the above range, the R / B ratio can be set within the above preferable range, and high light transmittance can be secured in the visible light region (400 to 700 nm). it can. In the agricultural film of the present invention, the average transmittance at 400 to 700 nm is preferably 55% or more, more preferably 60% or more.

  Another embodiment of the present invention relates to isoindolinone pigments and dioxazine violet (8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo [3,2-b: 3 ′, 2′-m ] Agricultural film containing triphenodioxazine). By including isoindoline and dioxazine violet, in addition to adjusting the R / B ratio, the R / G ratio can be adjusted by adjusting the absorption of green light. In this specification, the R / G ratio of green light and red light means the ratio of the transmitted light amount at 660 nm and the transmitted light amount at 555 nm.

  In cultivation experiments using LEDs and colored fluorescent lamps, it has been found that extreme red light enhancement does not necessarily lead to improved growth, but a balance of red light, green light and blue light is necessary. In particular, in experiments using fluorescent lamps, even in an environment with strong red light, it is becoming clear that blue light and green light are present to some extent in the cultivation environment. There has been an increasing interest in not only the / B ratio but also the R / G ratio. Under such circumstances, such light is specifically described in an improvement in cultivatability in a light environment having a higher R / G ratio than sunlight as well as a high R / B ratio, and in a form that can withstand actual use. There was a long-awaited way to get the environment. The invention of this embodiment makes it possible to adjust the R / G ratio in addition to adjusting the R / B ratio by using a specific combination of pigments.

  In the agricultural film of this embodiment, the R / B ratio is preferably 1.5 or more, and more preferably 1.7 or more. The R / G ratio is preferably 1.1 or more, more preferably 1.2 or more.

  In the agricultural film of the present invention, the content of dioxazine violet is 0.005 to 1.0% by weight, preferably 0.01 to 0.75% by weight, more preferably based on the weight of the whole agricultural film. Is 0.02 to 0.5% by weight. By setting the content of dioxazine violet in the above range, the R / G ratio can be set in the above preferable range, and high light transmittance can be secured in the visible light region (400 to 700 nm). . In the agricultural film of the present invention, the average transmittance at 400 to 700 nm is preferably 55% or more, more preferably 60% or more.

One preferred embodiment of the present invention is an agricultural polyolefin resin film comprising a polyolefin resin composition containing an isoindolinone pigment.
In the agricultural polyolefin-based resin film of the present invention, the R / B ratio is preferably 1.5 or more, and more preferably 1.7 or more.
The content of the isoindolinone pigment in the agricultural polyolefin-based resin film of the present invention is 0.01 to 3.0% by weight, preferably 0.05 to 2.0% by weight, further based on the weight of the whole film. Preferably it is 0.1 to 1.5 weight%.

Another preferred embodiment of the present invention is an agricultural polyolefin resin film comprising a polyolefin resin composition containing an isoindolinone pigment and dioxazine violet.
In the polyolefin resin film for agricultural use of this embodiment, the R / B ratio is preferably 1.5 or more, and more preferably 1.7 or more. The R / G ratio is preferably 1.1 or more, more preferably 1.2 or more.
In the polyolefin resin film for agriculture of the present invention, the content of dioxazine violet is 0.005 to 1.0% by weight, preferably 0.01 to 0.75% by weight, based on the total weight of the film. Preferably it is 0.02-0.5 weight%.

In the agricultural polyolefin-based resin film of the present invention, the isoindolinone pigment may be added to all layers, or may be added to some layers (intermediate layer, intermediate layer and outer layer, etc.).
In addition, in the polyolefin resin film for agricultural use of the present invention, isoindolinone pigment and dioxazine violet may be added to all layers, but also added to some layers (intermediate layer, intermediate layer and outer layer, etc.) You can also

  In the agricultural film and agricultural polyolefin resin of the invention, various additives usually used in agricultural films can be blended. Examples of these additives include anti-fogging agents, anti-fogging agents, weather resistance improvers (hindered amine light stabilizers, ultraviolet absorbers, etc.), weather resistance agents, infrared absorbers, heat retention agents, fillers, and metal organics. Oxidation of acid salts, basic organic acid salts and overbased organic acid salts, hydrotalcite compounds, epoxy compounds, β-diketone compounds, polyhydric alcohols, halogen oxyacid salts, sulfur-based, phenol-based and phosphite-based compounds Examples thereof include an inhibitor, a heat stabilizer, a lubricant, an antistatic agent, a colorant, and an antiblocking agent.

Antifogging agents include polyhydric alcohol partial esters composed of polyhydric alcohols and higher fatty acids, including various known nonionic surfactants, anionic surfactants, cationic surfactants, etc. Of these, silicone surfactants and fluorine surfactants are preferred. Specific examples of such an antifogging agent include, for example, nonionic surfactants such as sorbitan monostearate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan / alkylene glycol condensate and fatty acid. Sorbitan surfactants such as esters and glycerol monopalmitate, glycerol monostearate, glycerol monolaurate, diglycerol monopalmitate, glycerol dipalmitate, glycerol distearate, diglycerol monopalmitate monostearate Glycerin surfactants such as glycerol, monoglycerate, triglycerin monostearate, triglycerin distearate or alkylene oxide adducts thereof, polyethylene glycol monostearate, polyethylene glycol Polyethylene glycol surfactants such as coal monopalmitate, polyethylene glycol alkyl phenyl ether, and other trimethylolpropane surfactants such as trimethylolpropane monostearate, and pentaerythritol monopalmitate, pentaerythritol monostearate, etc. Erythritol surfactant, alkylene oxide adduct of alkylphenol; sorbitan / glycerin condensate and fatty acid ester, sorbitan / alkylene glycol condensate and fatty acid ester; diglycerin dioleate sodium lauryl sulfate, dodecylbenzenesulfonic acid Sodium, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauric acid laurylamide ethyl phosphate It can be exemplified triethylammonium cetyl ammonium iodide, oleyl amino diethylamine hydrochloride, and those containing dodecyl pyridinium salts, etc. and their isomers.

  As the antifogging agent, a fluorosurfactant, specifically, a surfactant obtained by substituting part or all of it with F in place of H bonded to C of the hydrophobic group of a normal surfactant, in particular, Surfactants containing perfluoroalkyl groups or perfluoroalkenyl groups can be used. Examples of the fluorine-containing compound having a perfluoroalkyl group include an anionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, a nonionic fluorine-containing surfactant, and a fluorine-containing oligomer. can give.

  As the hindered amine light stabilizer, a hindered amine light weathering agent usually blended for agricultural use can be used. For example, a hindered amine compound (having at least two piperidine ring structures in the molecule and having a molecular weight of 500 or more) Hereinafter, “piperidine ring-containing hindered amine compound”) can also be preferably used.

  Examples of the piperidine ring-containing hindered amine compound include bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl). ) Malonate, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butanetetra Carboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxy Rubonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2) , 6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4 , 6-Bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12-tetraaza Dodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) And hexamethylenediamine / dibromoethane condensate.

  In addition, commercially available hindered amine compounds, TINUVIN 770, TINUVIN 780, TINUVIN 144, TINUVIN 622LD, TINUVIN NOR 371, CHIMASSORB 119FL, CHIMASSORB 944 (above, manufactured by Ciba Geigy), Sanol LS-765 (manufactured by Sankyo Co., Ltd., R, MA, K) -68, MARK LA-68, MARK LA-62, MARK LA-67, MARK LA-57, LA-900, LA-81, NO-Alkyl-1 (above, manufactured by ADEKA), UV-3346, UV- 3529, UV-3581, UV-3853 (from Cytec), Hostabin N20, Hostabin N24, Hostabin N30, Hostabin 845, Hostabin NOW, Sandu A PR-31, Nairosutabbu S-EED (or more, manufactured by Clariant Japan KK), UVINUL5050H (or more, BASF Japan Co., Ltd.) and the like can be used. These piperidine ring-containing hindered amine compounds are used alone or in combination of two or more.

  Content of the said hindered amine type compound is 0.001 to 5 weight% with respect to 100 weight% of base resin of an agricultural film, Preferably it is 0.01 to 1 weight%. When the content is less than 0.001% by weight, a sufficient effect cannot be obtained, and when the content is more than 5% by weight, the effect is not improved, and the physical properties of the film are deteriorated.

式（１）において、Ｒ１及びＲ２は、それぞれ独立して、水素原子又はメチル基を表し、Ｒ３は水素原子又は炭素数１〜４のアルキル基を表し、好ましくは、Ｒ１及びＲ２はそれぞれメチル基であり、Ｒ３は水素原子である。 Moreover, the copolymer of ethylene (A) and the cyclic amino vinyl compound (B) represented by following formula (1) can also be added to the agricultural film of this invention.

In Formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably R1 and R2 are each a methyl group. And R3 is a hydrogen atom.

  The vinyl compound (B) represented by the formula (1) can be synthesized by a known method, for example, a method described in JP-B-47-8539, JP-A-48-65180, or the like.

  Representative examples of the vinyl compound (B) represented by the formula (1) include 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6. -Pentamethylpiperidine, 4-acryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, 4-acryloyl Oxy-1-butyl-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6- Pentamethylpiperidine, 4-methacryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1-butyl 2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-1-propyl-2,2,6,6-tetramethyl Examples include piperidine.

  As the preferred ethylene / cyclic aminovinyl compound copolymer, the ratio of (B) to the sum of ethylene (A) and cyclic aminovinyl compound (B) is 0.0005 to 0.85 mol%, More preferably, it is 0.001 to 0.55 mol%. That is, the preferred copolymer is one having a high light stability for a low content of the vinyl monomer having a hindered amine group in the side chain (cyclic aminovinyl compound (B)). When the concentration of the cyclic aminovinyl compound (B) is 0.0005 mol%, a sufficient light stabilizing effect is exhibited. On the other hand, when it exceeds 0.85 mol%, it tends to be substantially uneconomical.

  Further, the ethylene / cyclic aminovinyl compound copolymer is such that (B) is not continuous in two or more in the copolymer, and the ratio of being isolated is 83% or more based on the total amount of (B), Preferably it is 90% or more.

  The content of the ethylene / cyclic aminovinyl compound copolymer is preferably 0.5 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin constituting the film. If this content is less than the above range, the weather resistance is inferior because it is inferior.

  Examples of commercially available ethylene / cyclic aminovinyl copolymers that can be used include Novatec LD · XJ100H (manufactured by Nippon Polychem Co., Ltd.).

  In the present invention, by containing an ultraviolet absorber, a preferable light quality balance can be maintained for a long period of time by substantially cutting off ultraviolet rays, and a pest control effect can also be expected.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone) and the like. 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2- ( 2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′) 2- (2′-hydroxyphenyl) benzotriazoles such as .5′-dicumylphenyl) benzotriazole and 2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol; 5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4,6- Benzotriazole type ultraviolet absorbers such as di (tert-pentyl) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3 ′, 5′-ditertiarybutyl-4′-hydroxybenzoate, 2,4-ditertiary amylphenyl-3 ′, 5′-ditertiarybutyl-4′-hydroxybenzoate, hexadecyl-3,5-ditertiary Benzoates such as til-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β- Cyanoacrylates such as diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (4,6-diphenyl-1,3,5-triazin-2-yl)- Triazines such as 5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol And the like. These ultraviolet absorbers are used alone or in combination of two or more.
In the present invention, in particular, (2- [5-chloro (2H) -benzotriazol-2-yl] -4,6-di (tert-pentyl) phenol) alone or 2- [5-chloro By using in combination with (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, favorable light quality balance and pest control over a long period of time while imparting bleed-out resistance The effect can be expected.

  The ultraviolet absorber is preferably added in an amount of more than 0.001% by weight and less than 2% by weight, more preferably 0.01 to 1% by weight, based on 100% by weight of the base resin of the agricultural film. If the content is less than the above range, the effect of improving weather resistance is low, and if it exceeds the above range, there are problems such as a decrease in transparency due to bleeding out.

  By adding an infrared absorber to the agricultural film in the present invention, good heat retention can be imparted. As the infrared absorber, an inorganic compound (inorganic oxide, inorganic hydroxide, hydrotalcite, etc.) containing at least one atom of Mg, Ca, Al, Si and Li that is effective as a heat retaining agent can be used.

Especially, when the hydrotalcite infrared absorber represented by the following formula (2) is used, a film that is inexpensive and has good moldability can be obtained.
_{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 O (2)

In particular, when an infrared absorber represented by the following formula (3) is used, a film that is inexpensive and has good moldability can be obtained.
[Al ₂ (Li _(1-x) · M _{(x + y)} ) (OH) _{6 + y} ] ₂ (An ⁻ ) _{2 (1 + x) / n} · mH ₂ O (3) (wherein M is Mg and / or Zn A is an n-valent anion, m is 0 or a positive number, and x and y are in the range of 0 ≦ x <1, 0 ≦ y ≦ 0.5.)

  The method for obtaining the infrared absorber (heat retention agent) represented by the above formula (3) is not particularly limited, and commercially available products can be used, for example, DHT4A, SYHT-3 (manufactured by Kyowa Chemical Co., Ltd.). HT-P (manufactured by Sakai Chemical Co., Ltd.), Optima (manufactured by Toda Kogyo Co., Ltd.), Mizukarak (manufactured by Mizusawa Chemical Co., Ltd.), and the like.

  The infrared absorbent (heat retention agent) is inorganic fine particles having infrared absorbing ability, and these can be used alone or in combination of two or more. The inorganic fine particles that can be used are not particularly limited, but inorganic compounds containing at least one atom selected from the components: Si, Al, Mg, and Ca can be used. For example, magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium sulfate, aluminum sulfate, lithium phosphate, calcium phosphate , Magnesium silicate, calcium silicate, aluminum silicate, calcium aluminate, magnesium aluminate, sodium aluminosilicate, potassium aluminosilicate, calcium aluminosilicate, kaolin, clay, talc, mica, zeolite, hydrotalcite compounds and the like. These may be obtained by dehydrating crystal water.

  The inorganic fine particles may be natural products or synthetic products. The inorganic fine particles can be used without being limited by the crystal structure, crystal particle diameter, and the like.

  The content of the inorganic fine particles is preferably more than 0.1% by weight and less than 15% by weight, more preferably 1 to 12% by weight with respect to 100% by weight of the base resin of the agricultural film. If the content is less than the above range, the effect of improving heat retention is low, and if it exceeds the above range, there are problems such as a decrease in transparency.

  Examples of the metal species constituting the organic acid salt, basic organic acid salt and overbased organic acid salt of the metal include Li, Na, K, Ca, Ba, Mg, Sr, Zn, Cd, Sn, Cs, Examples of the organic acid include carboxylic acid, organic phosphoric acid, and phenol.

  Examples of the filler include silica, talc, aluminum hydroxide, hydrotalcite, calcium sulfate, calcium silicate, calcium hydroxide, and hydroxide in order to suppress stickiness of the film or to further increase the heat retention. Magnesium, kaolin clay, mica, alumina, magnesium carbonate, sodium aluminate, conductive zinc oxide, lithium phosphate and the like are used. One type of these fillers may be used, or two or more types may be used in combination.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate] and the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And propionic acid esters.

  Examples of the phosphite-based antioxidant include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl- 4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite.

  Examples of the colorant include phthalocyanine blue, phthalocyanine green, hansa yellow, alizarin lake, titanium oxide, zinc white, ultramarine blue, permanent red, quinacridone, and carbon black.

  The agricultural film of the present invention can contain the above-described components in combination, and can further contain the following optional components as necessary. Optional components include other stabilizers, impact resistance improvers, cross-linking agents, fillers, foaming agents, antistatic agents, nucleating agents, plate-out preventing agents, surface treatment agents, flame retardants, fluorescent agents, anti-glare agents Agents, bactericides, metal deactivators, mold release agents, pigments, processing aids and the like.

  The agricultural film of the present invention is each weighed in a necessary amount for blending various additives, and blending machines such as a ribbon blender, a Banbury mixer, a Henschel mixer, a super mixer, a single or twin screw extruder, a roll, and a kneading machine. Any other known blending machine or mixing machine may be used. In order to form the resin composition thus obtained into a film, a method known per se, for example, a melt extrusion molding method (including a T-die method and an inflation method), calendar processing, roll processing, extrusion molding processing, Blow molding, inflation molding, melt casting, pressure molding, paste processing, powder molding, and the like can be suitably used.

  About the thickness of the agricultural film of this invention, the thing of the range of 0.01-1 mm is preferable at the point of intensity | strength or cost, The thing of 0.05-0.5 mm is more preferable, More preferably, it is 0.05-0. .2 mm. If the thickness is within this range, an agricultural film free from problems of strength, molding and workability can be obtained.

Further, when the agricultural film of the present invention is an agricultural polyolefin resin film, it can be a multilayer film of 3 to 5 layers. The layer ratio constituting the three-layer film is preferably in the range of 1 / 0.5 / 1 to 1/5/1 in terms of moldability, transparency and strength, and 1/2/1 to 1/4/1. The range of is more preferable. Further, the ratio between the outer layer and the inner layer is not particularly specified, but it is preferable that the ratio is approximately the same because of the curl property of the obtained film.
In the case of polyolefin multilayer films, various additives such as the above weather resistance improvers (hindered amine light stabilizers, UV absorbers, etc.), weather resistance agents, infrared absorbers, and heat retention agents are added to all layers. It may also be added to some layers (intermediate layer, or intermediate layer and outer layer, etc.).

  The agricultural film of the present invention can form an antifogging coating film and other coating films. For example, an antifogging coating film may be formed on the inner surface when an agricultural film is coated on a house, and a dustproof coating film may be formed on the outer surface.

  Examples of the antifogging coating film include a composition mainly composed of a binder resin such as an inorganic colloid sol and / or a thermoplastic resin. Preferably, an antifogging coating film mainly comprising an inorganic colloid substance and a hydrophilic organic compound or an antifogging coating film comprising an inorganic colloid substance and an acrylic resin as main components can be used. Further, the binder resin may not be added, and an inorganic material such as colloidal silica or colloidal alumina may be laminated.

  As the inorganic colloidal sol, inorganic aqueous colloidal particles such as silica, alumina, water-insoluble lithium silicate, iron hydroxide, tin hydroxide, titanium oxide, barium sulfate were dispersed in water or a hydrophilic medium by various methods. And aqueous sols. Among these, silica sol and alumina sol are preferably used, and these may be used alone or in combination.

  As the inorganic colloid sol, it is preferable to select an average particle size in the range of 5 to 100 nm. In this range, two or more colloid sols having different average particle sizes may be used in combination. By setting the average particle size within this range, the coating does not become white and devitrified, and the stability of the inorganic colloidal sol is good.

  The amount of the inorganic colloidal sol is preferably 0.2 to 5 and preferably 0.5 to 4 in terms of the weight ratio as the solid content with respect to the total solid weight of the binder resin composition. That is, when the blending amount is too small, a sufficient antifogging effect may not be exhibited. On the other hand, when the blending amount is too large, the antifogging effect is not easily improved in proportion to the blending amount. The film formed later becomes cloudy and causes a phenomenon that the light transmittance of the film is lowered, and the film may be coarse and brittle, which is not preferable.

  Examples of the binder resin include acrylic resins, epoxy resins, urethane resins, and polyester resins. When the base film is a polyolefin film, it is particularly preferable to use an acrylic resin and / or a urethane resin from the viewpoint of compatibility with the polyolefin film, and more preferably (a) a hydrophilic acrylic heavy film described later. Those made of coalescence, (c) those made of a hydrophobic acrylic resin, and (e) those made of a hydrophobic acrylic resin and a polyurethane emulsion have their respective characteristics and are preferable.

  Examples of the acrylic resin include (a) one made of a hydrophilic acrylic polymer, (b) one made of a block copolymer containing a hydrophobic molecular chain block and a hydrophilic molecular chain block in one molecule, (c ) What consists of hydrophobic acrylic resin is mentioned. When the base film is a polyolefin-based film, (a) is particularly excellent in compatibility with the base film in terms of early antifogging and wetting, while (c) is preferable with the base film. It is excellent in compatibility.

  As the hydrophilic acrylic polymer (a), a hydroxyl group-containing vinyl monomer component is a main component (preferably 60 wt% to 99.9 wt%, more preferably 65 wt% to 95 wt%), acid Examples thereof include a copolymer containing 0.1 to 30% by weight of a group-containing vinyl monomer component, a partially neutralized product thereof, or a completely neutralized product thereof. Examples of the hydroxyl group-containing vinyl monomer component include hydroxyalkyl (meth) acrylates, such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Examples thereof include, but are not limited to, hydroxypropyl (meth) acrylate. These may be homopolymers, or may be copolymers of these hydroxyalkyl (meth) acrylates as main components and other monomers that can be copolymerized therewith.

  Examples of the acid group-containing monomer copolymerizable with these hydroxyalkyl (meth) acrylates include carboxylic acids, sulfonic acids and phosphonic acids, and (meth) acrylic acid belonging to carboxylic acids is particularly preferred.

  Examples of other copolymer components include styrene, vinyl toluene, vinyl chloride, vinylidene chloride, vinyl oxide, (meth) acrylic acid esters, N, N-dimethylaminoethyl (meth) acrylamide, vinyl pyridine, and the like. .

  As the hydrophobic acrylic resin (c), at least a total of 60% by weight of a monomer comprising an alkyl ester of acrylic acid or methacrylic acid, or a single unit of an alkyl ester of acrylic acid or methacrylic acid and an alkenylbenzene. A monomer mixture and 0 to 40% by weight of a copolymerizable α, β-ethylenically unsaturated monomer are obtained by emulsion polymerization in an aqueous medium, for example, in the presence of an emulsifier, under normal polymerization conditions. And water dispersible polymers or copolymers.

  Examples of alkyl esters of acrylic acid or methacrylic acid used in the production of hydrophobic acrylic resins include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid-n-propyl ester, acrylic acid isopropyl ester, acrylic acid-n- A butyl ester etc. are mentioned, Generally, a C1-C20 acrylic acid alkyl ester and / or a C1-C20 methacrylic acid alkyl ester of an alkyl group are used. Examples of alkenylbenzenes include styrene, α-methylstyrene, vinyltoluene and the like.

  Examples of α, β-ethylenically unsaturated monomers used to obtain hydrophobic acrylic resins include α, β such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and itaconic acid. -Ethylenically unsaturated carboxylic acids; α, β-ethylenically unsaturated sulfonic acids such as ethylene sulfonic acid; 2-acrylamido-2-methylpropanoic acid; α, β-ethylenically unsaturated phosphonic acids; acrylic acid or methacrylic acid Hydroxyl group-containing vinyl monomers such as hydroxyethyl; acrylonitriles; acrylic amides; glycidyl esters of acrylic acid or methacrylic acid, and the like. These monomers may be used alone or in combination of two or more, and are preferably used in the range of 0 to 40% by weight. If the amount used is too large, the antifogging performance may be lowered, which is not preferable.

  The acrylic resin is a known emulsifier, for example, an anionic surfactant, a cationic surfactant, or a nonionic surfactant, in the presence of one or more kinds in an aqueous medium. It can be obtained by a method of emulsion polymerization, a method of polymerization using a reactive emulsifier, a method of polymerizing based on an oligo soap theory without containing an emulsifier.

  Examples of the polymerization initiator preferably used for the production of the acrylic resin include persulfates such as ammonium persulfate and potassium persulfate. These can be used in the range of 0.1 to 10% by weight based on the total amount of monomers charged.

  It is particularly preferable to use a hydrophobic acrylic resin having a glass transition temperature of 35 to 80 ° C. If the glass transition temperature is too low, the inorganic colloidal particles are agglomerated several times and tend to be in a non-uniform dispersion state. If it is too high, it is difficult to obtain a transparent uniform coating.

  The hydrophobic acrylic resin is preferably used as an aqueous emulsion. An aqueous emulsion obtained by polymerization of each monomer in an aqueous medium may be used as it is, or may be diluted by adding a liquid dispersion medium to this, and also produced by the above polymerization. A polymer may be collected separately and re-dispersed in a liquid dispersion medium to form an aqueous emulsion.

  On the other hand, examples of the (d) urethane-based resin include polyether-based, polyester-based, and polycarbonate-based anionic polyurethane aqueous compositions and emulsions. When the base film is a polyolefin-based film, a polycarbonate-based anionic polyurethane emulsion is preferable from the viewpoint of adhesion of the anti-fogging coating film to the base film, water resistance and scratch resistance, and further anti-fogging coating. A polycarbonate-based anionic polyurethane emulsion containing a silanol group is more preferable from the viewpoints of improvement in water resistance and scratch resistance of the film, time until the antifogging property is developed, and antifogging durability. These may be used alone or in combination of two or more.

  A polycarbonate-based anionic polyurethane emulsion containing a silanol group comprises a polyurethane resin containing at least one silanol group in the molecule and a strongly basic tertiary amine as a curing catalyst. Refers to a colloidal dispersion system (emulsion) in which the silanol group-containing polyurethane resin and the strongly basic tertiary amine are dissolved in the aqueous phase, or a colloidal dispersion system in which fine particles are dispersed.

  It is preferable that the amount of the polyurethane aqueous composition is 0.01 or more and 2 or less, more preferably 0.01 or more and 1 or less with respect to the hydrophobic acrylic resin in terms of solid content by weight. When it is less than 0.01, it is difficult to improve the scratch resistance, and it takes a long time until the antifogging property is exhibited, and it is difficult to exhibit a sufficient antifogging effect. In addition, when it is too much, not only the scratch resistance is difficult to improve in proportion to the blending amount, but the coating film formed after coating tends to become cloudy and lower the light transmittance, which is also disadvantageous in terms of cost. It is not preferable.

  When preparing an antifogging agent composition for forming an antifogging coating film, an anionic surfactant, a cationic surfactant, a nonionic surfactant, a polymer surfactant, etc. An activator can be added. The following can be used as such a surfactant.

  Anionic surfactants include fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfones such as sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate Acid salt and alkyl naphthalene sulfonate salt; naphthalene sulfonic acid formalin condensate; dialkyl sulfosuccinate salt; dialkyl phosphate salt; polyoxyethylene sulfate salt such as sodium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene alkylphenyl ether sulfate Can be mentioned.

  Cationic surfactants include: ethanolamines; laurylamine acetate, triethanolamine monostearate formate; amine salts such as stearamide ethyl diethylamine acetate; lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dilauryldimethyl And quaternary ammonium salts such as ammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and the like.

  Nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octylphenol and polyoxyethylene nonylphenol. Alkylaryl ethers; polyoxyethylene acyl esters such as polyethylene glycol monostearate; polypropylene glycol ethylene oxide adducts; sorbitan fatty acid esters such as sorbitan monostearate, sorbitan monopalmitate, sorbitan monobenzoate; diglycerin monopalmi Diglycerol fatty acid esters such as tate and diglycerol monostearate; glycerol monostearate Glycerin fatty acid esters such as pentaerythritol monostearate, etc .; dipentaerythritol fatty acid esters such as dipentaerythritol monopalmitate; sorbitan monopalmitate half adipate, diglycerin monostearate half Sorbitan such as glutamate and diglycerin fatty acid / dibasic acid esters; or condensates thereof with alkylene oxide such as ethylene oxide and propylene on oxide such as polyoxyethylene sorbitan monolaurate and polyoxypropylene sorbitan monostearate Etc .; Polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene stearamide, etc. Carboxymethyl ethylene alkyl amine fatty acid amides; sugar esters.

  Examples of the polymer surfactant include polyacrylate, polymethacrylate, and cellulose ethers.

  The addition of the surfactant can easily and quickly disperse the binder resin and the inorganic colloid sol, and when used in combination with the inorganic colloid sol, imparts hydrophilicity to the surface of the hydrophobic polyolefin resin film. Fulfills the function. The addition amount of the surfactant is preferably selected in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin solid content. If the amount of the surfactant added is too small, it takes time to sufficiently disperse the resin and the inorganic colloid sol, and the antifogging effect in combination with the inorganic colloid sol cannot be sufficiently exhibited. If the amount added is too large, the transparency of the coating will decrease due to the bleed-out phenomenon on the coating surface formed after coating, and if it is noticeable, it may cause deterioration of the blocking resistance of the coating or decrease the water resistance of the coating. .

  A cross-linking agent can be added when preparing an antifogging agent composition for forming an antifogging coating film. A crosslinking agent has an effect which bridge | crosslinks acrylic resin especially and improves the water resistance of a coating film. Examples of the crosslinking agent include phenol resins, amino resins, amine compounds, aziridine compounds, azo compounds, isocyanate compounds, epoxy compounds, silane compounds, etc., but particularly amine compounds and aziridine compounds. Epoxy compounds can be preferably used.

  A liquid dispersion medium can be mix | blended with the anti-fogging agent composition used for this invention as needed. Such a liquid dispersion medium includes a hydrophilic or water-miscible solvent containing water, water; monohydric alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, and glycerin. Examples: cyclic alcohols such as benzyl alcohol; cellosolve acetates; ketones and the like. These liquid dispersion media may be used alone or in combination.

  If necessary, the antifogging agent composition can be mixed with conventional additives such as an antifoaming agent, a plasticizer, a film forming aid, a thickening agent, a pigment, and a pigment dispersant. Further, as a binder component other than the acrylic resin, for example, a polyether-based, polycarbonate-based, or polyester-based water-dispersible urethane resin may be mixed.

  In order to form an antifogging coating film on the surface of a base film, generally a solution or a dispersion of an antifogging composition is applied to a doctor blade coating method, a roll coating method, a dip coating method, a spray coating method, or a rod coating method, respectively. A known coating method such as a bar coating method, a knife coating method, or a brush coating method may be employed and dried after coating. As a drying method after coating, either a natural drying method or a forced drying method may be employed. When the forced drying method is employed, the drying method is usually 50 to 250 ° C., preferably 70 to 200 ° C. Good. For heating and drying, an appropriate method such as a hot air drying method, an infrared drying method, a far infrared drying method, and an ultraviolet curing method may be employed, and it is advantageous to adopt the hot air drying method in consideration of the drying speed and stability. is there.

  The thickness of the anti-fogging coating film may be selected based on 1/10 or less of the base film, but is not necessarily limited to this range. If the thickness of the coating film is larger than 1/10 of the base film, there is a difference in flexibility between the base film and the coating film, so that a phenomenon such as peeling of the coating film from the base film is likely to occur. Moreover, the phenomenon that a crack occurs in the coating film to reduce the strength of the base film occurs, which is not preferable.

  Moreover, when the adhesiveness of the base film and the coating film derived from an antifogging agent composition is not enough, you may surface-treat to a base film. Examples of the surface treatment method include corona discharge treatment, sputter etching treatment, sodium treatment, and sandblast treatment. In the corona discharge treatment method, discharge is performed between a needle-like or knife-edge electrode and a counter electrode, and a sample is placed between the electrodes, and the film surface contains oxygen such as aldehyde, acid, alcohol peroxide, ketone, ether, etc. This is a process for generating a functional group. In the sputter etching process, a sample is placed between electrodes that are performing low-pressure glow discharge, and a large number of fine protrusions are formed on the film by the impact of positive ions generated by the glow discharge. In the sandblasting process, fine sand is sprayed on the film surface to form a large number of fine irregularities on the surface. Among these surface treatments, corona discharge treatment is preferable from the viewpoints of adhesion to the coating layer, workability, safety, cost, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to the following examples, unless the summary is exceeded.

(1) Preparation of polyolefin-based resin multilayer film 100 mmφ (made by Pla Koken Co., Ltd.) is used for a three-layer die as a three-layer inflation molding device, and the extruder has two outer tube inner layers of 30 mmφ (made by Pla Giken Co., Ltd.). The inner layer is 40 mmφ (manufactured by Plastic Giken Co., Ltd.), the outer inner layer extruder temperature is 180 ° C., the intermediate layer extruder temperature is 170 ° C., the die temperature is 180 to 190 ° C., the blow ratio is 2.0 to 3.0, A three-layer laminated film composed of the components shown in Table 1 was obtained at a speed of 3 to 7 m / min and a thickness of 0.10 mm. Since these films are used with the end of the tube cut open when the house is stretched, the tube outer layer during film formation becomes the inner layer (inner surface) of the house when stretched when unfolded.
Table 1 shows the composition of the substrate.

[Composition] The addition amount is as described in each table.
HP-LDPE: branched polyethylene produced with a high-pressure radical catalyst (MFR: 0.7 g / 10 min, density 0.924) Novatec LD “LF240” manufactured by Nippon Polychem
Metallocene PE: ethylene / α-olefin copolymer produced with a metallocene catalyst (MFR: 2.0 g / 10 min, density 0.913) Kernel “KF270” manufactured by Nippon Polychem
EVA1: Ethylene / vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 2 g / 10 min)

Kimasorb 944: Light stabilizer synthetic hydrotalcite A manufactured by Ciba Specialty Chemicals Co., Ltd .: “DHT4A” manufactured by Kyowa Chemical Co., Ltd.
Ethylene / Cyclic aminovinyl copolymer: “NOVATEC LD · XJ100H” manufactured by Nippon Polychem Co., Ltd. MFR = 3 g / 10 min (190 ° C., JIS-K6760) Density = 0.931 g / cm ³ (JIS-K6760) Cyclic amino Vinyl compound content = 5.1% by weight (0.7 mol%) Percentage of cyclic aminovinyl compound present in isolation = 90 mol% Melting point = 111 ° C.

Pigment master batch A: PE master batch (manufactured by Dainichi Seika Kogyo Co., Ltd.) containing 30% by weight of isoindolinone pigment A (orange pigment) is used. Pigment master batch B: Isoindolinone pigment B (yellow) Pigment master batch containing 30% by weight (manufactured by Dainichi Seika Kogyo Co., Ltd.) Pigment master batch C: PE master batch containing 1% by weight of dioxazine violet (Daiichi Seika Kogyo Co., Ltd.) Fluorescent substance A: SMART LIGHT RL1000 (wavelength conversion fluorescent substance) (manufactured by BASF)

(2) Surface treatment of film The outer layer surface of the obtained tubular film was subjected to corona discharge treatment at a discharge voltage of 120 V, a discharge current of 4.7 A, and a line speed of 10 m / min, and the “wetting index” according to JIS-K6768 was measured. The value was confirmed.

(3) Formation of anti-fogging coating film (anti-fogging coating type)
The main component (silica sol and / or alumina sol) shown in Table 1, a thermoplastic resin, a crosslinking agent, and a liquid dispersion medium were blended to obtain an antifogging agent composition.
The antifogging agent composition was blended as follows.
Inorganic colloidal sol (colloidal silica) 4.0
Thermoplastic resin (Sanmor SW-131) 3.0
Cross-linking agent (TAZM) 0.1
Dispersion medium (water / ethanol = 3/1) 93
(Note) The amount of inorganic colloidal sol is indicated by the amount of inorganic particles, and the amount of thermoplastic resin is indicated by the solid content of the polymer.
Colloidal silica: Snowtex 30 manufactured by Nissan Chemical Co., Ltd., average particle size 15 mμ
Sunmole SW-131: acrylic emulsion T.E. A. Z. M: The above-described antifogging agent composition was applied to the surface of a base film surface-treated with an aziridine compound (2) manufactured by Mutual Pharmaceutical Co., Ltd. using a # 5 bar coater. The applied film was kept in an oven at 80 ° C. for 1 minute to volatilize the liquid dispersion medium to form an antifogging coating film. The thickness of the coating film of each obtained film was about 1 μm.

  This time, a test was performed using a type (film thickness: 100 μm) provided with an antifogging coating film, but the same effect can be obtained with a type in which an antifogging agent is mixed. Moreover, the same effect is acquired even if it is a combination other than the resin used this time, an additive, or film thickness different from this time, unless the summary is changed.

[Examples 1-2]
In the formulation of the multilayer film shown in Table 1, 5% by weight and 2.5% by weight of the pigment master batch A were added to the intermediate layer to prepare multilayer films of Examples 1 and 2, respectively.

[Example 3]
In the formulation of the multilayer film shown in Table 1, 5% by weight of the pigment master batch B was added to the intermediate layer to prepare the multilayer film of Example 3.

[Example 4]
In the formulation of the multilayer film shown in Table 1, 1% by weight of pigment master batch A and 5% by weight of pigment master batch C were added to the intermediate layer to prepare the multilayer film of Example 4.

[Example 5]
In the formulation of the multilayer film shown in Table 1, 2% by weight of pigment master batch A and 5% by weight of pigment master batch C were added to the intermediate layer to prepare a multilayer film of Example 5.

[Example 6]
In the composition of the multilayer film shown in Table 1, 3% by weight of pigment master batch A and 5% by weight of pigment master batch C were added to the intermediate layer to prepare a multilayer film of Example 6.

[Example 7]
In the formulation of the multilayer film shown in Table 1, 1% by weight of pigment master batch B and 5% by weight of pigment master batch C were added to the intermediate layer to prepare a multilayer film of Example 7.

[Example 8]
In the multilayer film formulation shown in Table 1, 1.25% by weight of pigment master batch B and 5% by weight of pigment master batch C were added to the intermediate layer to prepare a multilayer film of Example 8.

[Example 9]
In the multilayer film formulation shown in Table 1, 1.5% by weight of pigment master batch B and 5% by weight of pigment master batch C were added to the intermediate layer to prepare a multilayer film of Example 9.

[Comparative Example 1]
In the composition of the multilayer film shown in Table 1, 5% by weight of pigment master batch C was added to the intermediate layer to prepare a multilayer film of Comparative Example 1.

[Comparative Example 2]
In the composition of the multilayer film shown in Table 1, 2.5% by weight of the fluorescent substance A was added to the intermediate layer to prepare a multilayer film of Comparative Example 2.

[Comparative Example 3]
In the composition of the multilayer film shown in Table 1, 1.25 wt% of the fluorescent substance A was added to the intermediate layer to prepare a multilayer film of Comparative Example 3.
[Example 10]

  In the formulation of the multilayer film shown in Table 1, 1.5% by weight of pigment master batch A and 5% by weight of pigment master batch C are added to the intermediate layer, and seed 740 (Sipro Kasei Co., Ltd.) is used as an ultraviolet absorber. The multilayer film of Example 10 was prepared by adding 1.2 wt% to the intermediate layer and 0.3 wt% tinuvin 326 (BASF) to the intermediate layer.

  For each sample, the following optical characteristics were measured.

(1) Total light transmittance A multilayer film obtained by three-layer inflation molding (after forming (coating) an antifogging coating on the surface of the house inner layer) is a spectrophotometer (manufactured by Shimadzu Corporation, UV-2450 type: Measured with an integrating sphere unit), the value at each wavelength is shown.

(2) Illuminance measurement at each wavelength with a spectroradiometer A multilayer film obtained by three-layer inflation molding (after forming an antifogging coating on the inner layer side surface (after coating)) is sampled 30 cm square, and the spectroradiometer It was measured in a state of covering the light receiving portion (manufactured by Eiko Seiki Co., Ltd., MS-720 type), and the transmitted light amount (Irradiance (μmol / m ² / s / μm)) at each wavelength was shown. The measurement was carried out in Nagoya City on March 31, 2014 in fine weather. At the time of measurement, measure each sample without covering the sample film, carefully measure and compare while confirming that the illuminance is stable (the illuminance of the light source is the same). It was.
Furthermore, using the measurement data, visible light average transmitted light amount of 400 to 700 nm, R / B ratio (660 nm transmitted light amount / 460 nm transmitted light amount), R / G ratio (660 nm transmitted light amount / 555 nm transmitted light amount), Was measured.

  FIG. 1 shows the total light transmittance of 200 to 700 nm for Examples 1 to 3 and Comparative Example 4 (general agricultural polyolefin film agristor manufactured by Mitsubishi Plastics Agridream Co., Ltd.). From FIG. 1, the multilayer films of Examples 1 to 3 containing an isoindolinone pigment absorb blue light around 460 nm, while the transmittance of red light around 660 nm is comparable to that of a general agricultural polyolefin film. It is shown that.

  The total light transmittance of 200 to 700 nm for Examples 4 to 6 and Comparative Example 4 is shown in FIG. From FIG. 2, the multilayer films of Examples 4 to 6 containing isoindolinone pigment and dioxazine violet absorb blue light near 460 nm and green light near 550 nm, while red light near 660 nm. It is shown that the transmittance of this is comparable to that of Comparative Example 4.

  The total light transmittance of 200 to 700 nm for Examples 7 to 9 and Comparative Example 4 is shown in FIG. From FIG. 3, the multilayer films of Examples 7-9 containing isoindolinone pigment and dioxazine violet absorb blue light near 460 nm and also absorb green light near 550 nm, while red light near 660 nm. It is shown that the transmittance of this is comparable to that of Comparative Example 4.

  The measurement data of the total light transmittance of Comparative Examples 1 to 4 are shown in FIG. From FIG. 4, Comparative Example 1 in which only dioxazine vit is added as a pigment absorbs green light near 550 nm, but light near 460 nm is almost the same as Comparative Example 4 (general agricultural polyolefin film). It has been shown not to absorb.

In FIG. 5, the spectroradiometer measurement data of 350-700 nm about Examples 1-3 and the comparative example 3 are shown. In FIG. 6, the spectroradiometer measurement data of 350-700 nm about Examples 4-6 and the comparative example 3 are shown. In FIG. 7, the spectroradiometer measurement data of 350-700 nm about Examples 7-9 and the comparative example 3 are shown. In FIG. 8, the spectroradiometer measurement data of 350-700 nm about Comparative Examples 1-4 are shown.
Moreover, in Tables 2-5, about Examples 1-3, Examples 4-6, Examples 7-9, and Comparative Examples 1-4, respectively, the average transmitted light amount of 400-700 nm, R / B ratio, R / G is shown. Moreover, the graph which compared these numerical values about each film is shown in FIG.

  From Tables 2 to 5, the multilayer films of Examples 1 to 9 have an R / B ratio of 1.5 or more, and the multilayer films of Examples 4 to 9 have an R / G ratio of 1.2 or more. It is shown that there is.

Next, with respect to Example 10 and Comparative Example 5 (general agricultural polyolefin UV cut film (Easter UV cut)), the fastness resistance test was performed under the following conditions.
(A) Conditions of 60 ° C. and humidity 70%, light having a wavelength distribution of 295 to 780 nm with an irradiation intensity of 80 mW / cm ² for 5 hours (b) conditions of 30 ° C. and 98% (with water spray by shower) The load test was carried out for 230 hours in a 1 hour cycle without irradiation.
10 and 11 show the initial total light transmittance of Example 10 and Comparative Example 5 and the total light transmittance after the fastness test. 10 and 11 show that the multilayer film of Example 10 has no significant change in absorption of blue light and green light even after the fastness test.

As shown in the above Examples, the agricultural polyolefin-based resin films (Examples 1 to 3) containing the isoindolinone pigment absorb blue light, while the red light is the same as the general agricultural polyolefin-based film. It penetrates to the extent that it exhibits an R / B ratio of 1.5 or greater.
Further, the agricultural polyolefin resin films (Examples 4 to 9) containing an isoindolinone pigment and dioxazine violet absorb blue light and green light, while red light is a general agricultural polyolefin resin. It permeates to the same extent as the film, shows an R / B ratio of 1.5 or more, and further shows an R / G ratio of 1.2 or more.
Here, at the time of data measurement of the example, the R / B ratio and R / G ratio of sunlight of the spectroradiometer at the time of fine weather were about 1.33 and 1.05. On the other hand, the wavelength conversion films (Comparative Examples 2 and 3) have an R / B ratio and an R / G ratio of about 1.7 to 2.2 and 1.2 to 1.3, respectively, under sunlight. The light environment has a high contrast, R / B ratio, and R / G ratio (Table 5).
Therefore, by using the agricultural polyolefin film of the present invention, a light environment having high sunlight contrast, R / B ratio, and R / G ratio can be obtained as in the case of using the wavelength conversion film, and for plants. It is possible to provide an ideal light quality balance.
Further, the agricultural polyolefin-based resin film of the present invention has no significant change in the absorption of blue light and green light even after the fastness test, and the light quality of the R / B ratio and R / G ratio after stretching outdoors. It is possible to maintain balance.

Claims (4)

  Agricultural film containing isoindolinone pigment.   The agricultural film according to claim 1, further comprising dioxazine violet.   An agricultural polyolefin resin film comprising a polyolefin resin composition containing an isoindolinone pigment.   The polyolefin resin film for agriculture according to claim 3, wherein the polyolefin resin composition contains dioxazine violet.

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