JP2011115073A - Agricultural polyolefin film, and method for cultivating plant using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an agricultural film suitable for light supplement cultivation. <P>SOLUTION: This agricultural film is obtained by forming an anti-fogging agent layer having inorganic minute particles and/or synthetic resin binder as the main ingredient, on a polyolefin film containing 0.1-5 wt.% of fluorescent matter of formula (1). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a resin composition containing 0.1 to 5% by weight of a specific fluorescent material that can emit a visible light component having a wavelength of at least 600 to 700 nm as a wavelength component, which is used in a facility for horticulture using sunlight. The present invention relates to an agricultural polyolefin multilayer or single-layer film comprising a layer made of an anti-fogging agent composition mainly composed of inorganic fine particles and / or a synthetic resin binder. The agricultural film of the present invention shows a good anti-fogging action while suppressing the antagonistic action with the anti-fogging agent, and shows a very good wavelength conversion effect in order to suppress irregular reflection due to water droplets condensed on the film surface. .

  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. Onitsuna white lice, southern blue thrips, citrus white thrips are typical pests of crops widely cultivated in the house such as tomatoes, cucumbers, melons, strawberries, flower buds, etc., in addition to food damage, leaf and fruit discoloration, deformation 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 a problem of electric energy cost and local irradiation, for example, a wavelength conversion film as disclosed in JP-A-7-123870 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. Actually, the perylene wavelength conversion material used in the examples has a low effect persistence and is also a polyester-based material. Although compatible with the resin, it was not compatible with the polyolefin-based resin, and there was a practical problem such that a wide film could not be formed.

  In addition, wavelength conversion materials are often unstable to heat, etc. Even if the compound has a wavelength conversion effect, the processing temperature is lowered to a temperature level at which it cannot actually be processed by thermal decomposition or does not decompose. However, there are cases where the wavelength conversion effect is inferior due to the modification due to heat. In addition, improper selection of the resin results in an imbalance in resin fluidity, which greatly impairs transparency and offsets the increase in visible light components due to the wavelength conversion effect. In some cases, it was sufficient, or conversely, the photosynthetic production volume was reduced and the cultivatability decreased. Thus, there has been a demand for a specific method for producing an agricultural polyolefin film that can be formed into a wide width while achieving both high transparency and sustainability of the wavelength conversion effect.

  Furthermore, the wavelength conversion efficiency is important because the wavelength converting material absorbs light energy and re-radiates it as light that is easily absorbed by long-wavelength plant photoreceptors. Examples of conventional wavelength converting substances are mentioned as to whether or not there is a wavelength conversion effect, but there is no mention of how to obtain high wavelength conversion efficiency depending on specific embodiments, and specific examples as agricultural films. There was a need for a creation method.

  On the other hand, as a method of increasing the yield per unit area by the cultivation method, for example, in the hydroponic cultivation of roses, JP 3-191716 A takes only the buds of the branches that were initially extended in the initial stage of cultivation, The branch is artificially bent near the root and maintained in a lying state, and basal shoots generated from the vicinity of the root are grown as branches, cut and flowered from the base where the leaves are not attached, and after the first flowering Discloses a cultivation method in which basal shoots generated from the bases without leaves of all branches not flowered are grown as branches and cut and flowered from the bases without leaves of the branches. This cultivation method is named as an arching method, and is spreading with the spread of hydroponics technology.

  Such a cultivation method is very useful and popular because it can stably harvest high-quality roses compared to ordinary soil cultivation, but the bent branch is used as a source of photosynthesis. There is a limit to the increase in yield per unit area for use, and specific proposals for further methods of increasing yield have been sought.

JP 7-123870 A JP 2007-135583 A Japanese Patent Laid-Open No. 3-191716

  In this way, even if the conventional technology related to cultivation using the wavelength conversion film was used, it was rare that a satisfactory effect was actually obtained, so feasible cultivation technology using horticultural facilities Was demanded.

  The present inventor, in supplementary light cultivation using an agricultural house with a small initial investment, with a coating material having a special light transmission characteristic, the wavelength that the irradiation range is wider than the supplementary device without incurring electric energy costs We studied a means that can maintain high wavelength conversion efficiency while taking advantage of the characteristics of the conversion film and can effectively supplement light over a long period of time. A specific fluorescent substance is effective over a long period of time. However, it has been found that this fluorescent substance has an anti-fogging agent and an antagonistic action. As a result of further studies by the inventor, a means capable of avoiding this antagonism could be found.

  Thus, the present invention provides a substrate film comprising a resin composition containing 0.1 to 5% by weight of a specific fluorescent material capable of emitting light containing a visible light component of at least 600 to 700 nm as a wavelength component. A polyolefin-based multilayer or single-layer agricultural film characterized by forming a layer comprising an anti-fogging agent composition mainly composed of inorganic fine particles and / or a synthetic resin binder, or the specific fluorescent material By using supplementary light cultivation for cultivated plants using a breathable crop cultivation material containing thermoplastic resin, it is possible to effectively increase the yield, and to further prevent diseases and insects and protect internal materials from deterioration. The present inventors have found a specific method capable of avoiding the influence on the flower color while obtaining an effect.

  Furthermore, in the present invention, when combined with a specific ultraviolet absorber, not only the sustainability of the wavelength conversion effect but also the performance suitable as an agricultural material can be exhibited in a balanced manner. In addition, the present invention can particularly promote the growth promotion effect of Rosaceae over a long period of time, and since it does not affect the color development of red flowers, high-quality production of florets and an increase in yield per unit area The present invention relates to a method for cultivating crops that contributes to coexistence with the plant and is excellent not only in preventing deterioration of materials in the house but also in controlling pests. Further, the present invention relates to a breathable agricultural material for cultivation using the resin composition, and also relates to a method for efficiently cultivating the film as a house lining or lining film.

  The polyolefin film for agriculture of the present invention has very good antifogging property on the inner layer side of the house, while preventing the occurrence of diseases caused by the deterioration of cultivation due to insufficient light quantity due to light scattering by water droplets and the drop of water droplets, Agricultural materials that can achieve a high cropping effect, and when combined with a specific UV absorber, a high cropping improvement effect can be obtained for a long time without affecting the rose color. Very preferred. The agricultural material of the present invention can be suitably used as agricultural films and nets for house, tunnel, mulching, bag hanging and the like.

Initial transmittance of various fluorescent materials (150 μm thick PO film) Transmittance after load test (90 hours) of various fluorescent materials (150 μm thick PO film) Effect of wavelength conversion film under sunlight Graph showing antagonism between fluorescent substance and anti-fogging agent Transmittance after load test of wavelength conversion film (Example 3) Transmittance after load test of wavelength conversion film (Example 2) Embodiment of Comparative Example Using LED 1 ... Stock Company 2 ... Branch that has maintained the lying state Example Embodiments Using Films of the Invention Preferred example of using the polyolefin film for agriculture of the present invention

  Hereinafter, the present invention will be described in detail.

The substrate film for agricultural polyolefin film of the present invention is characterized by comprising a polyolefin resin composition containing a fluorescent material represented by the following formula (1).

(In formula, R1-R2 represents a hydrogen atom or a C1-C10 alkyl group each independently.)
Among these, R1 and R2 are preferably methyl groups.

The compound of formula (1) can be synthesized by a known method. For example, it can also be synthesized by the method described in Chemistry Letters 2000, P1426 “Synthesis and Nonlinear Optical Properties of p- (Dimethylamino) benzylidene Dyes Containing Different Acceptors”. I can do it. In that case, the compound of following formula (3) may be produced | generated as a by-product.

(Wherein R8 to R9 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)
In that case, the ratio of the formula (1) / the formula (3) is preferably 60% or more, preferably 80% or more, and more preferably 90% or more from the viewpoint of compatibility with the polyolefin resin.

  In the present invention, the polyolefin resin composition constituting the base film contains 0.1 to 5% by weight, preferably 0.5 to 3% by weight, of the fluorescent material represented by the formula (1). The base film may be a single layer or a multilayer, but in the case of a multilayer, the fluorescent material does not need to be blended in all layers. In the case of three layers often used as an agricultural film, it is preferable to blend in the intermediate layer because it is less susceptible to the environment due to weather resistance and the like. In the case of multiple layers, the content of the fluorescent material indicates the amount of the resin composition in all layers.

  Examples of the polyolefin resin used in the present invention include an α-olefin homopolymer, a copolymer of a different monomer mainly containing an α-olefin, an α-olefin and a conjugated diene or a non-conjugated diene, etc. And polyunsaturated compounds, acrylic acid, methacrylic acid, copolymers with vinyl acetate, etc., such as high density, low density or linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene- Examples include butene copolymer, ethylene-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.

  Moreover, in this invention, it is preferable to use the ethylene-alpha-olefin copolymer resin obtained by copolymerizing with a metallocene catalyst as at least one component of 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. It can be obtained by (Method A) or (Method B).

  (Method A) JP-A-58-19309, JP-A-59-95292, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008 , JP-A-60-35009, JP-A-61-130314, JP-A-3-163088, European Patent Application No. 420436, US Pat. No. 5,555,438 and International Publication WO91. The method described in US Pat. No. 04247, for example, a metallocene catalyst, particularly a metallocene / alumoxane catalyst, or a metallocene compound and a metallocene compound as disclosed in, for example, International Publication No. WO92 / 01723 A catalyst comprising a compound that reacts with the compound to form stable ions, or further, JP-A-5-295020, JP-A-5-2 Using a catalyst in which a metallocene compound is supported on an inorganic compound, as described in No. 5022, etc., a copolymer obtained from ethylene as a main component and an α-olefin having 4 to 20 carbon atoms as a subcomponent is obtained. In this method, copolymerization is performed so that the density of the polymer is 0.880 to 0.930 g / cm 3. Examples of the polymerization method include a high-pressure ion polymerization method, a solution method, a slurry method, and a gas phase method. In these, it is preferable to manufacture by a high pressure ion polymerization method.

The high-pressure ion polymerization method is described in JP-A-56-18607 and JP-A-58-25106, but the pressure is 100 kg / cm ² or more, preferably 300 to 1500 kg / cm. ^{2 and produced} at a temperature of 125 ° C. or higher, preferably 150 to 200 ° C. by a high pressure ion polymerization method.

(Method B) Metallocene catalyst component and organoaluminum oxy compound catalyst component described in JP-A-6-9724, JP-A-6-136195, JP-A-6-136196, and JP-A-6-207057 In the presence of an olefin polymerization catalyst, various conditions in the gas phase, slurry, or solution liquid phase, including a particulate carrier, and optionally an organoaluminum compound catalyst component and an ionized ionic compound catalyst component And ethylene and an α-olefin, specifically, an α-olefin having 3 to 20 carbon atoms, are copolymerized so that the density of the resulting copolymer is 0.900 to 0.930 g / cm ³ cm ³ . Method.

  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) The 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 debate proceedings 2P1C09 (Showa 63) ”, and the like. That is, first, the target polyethylene is completely dissolved once in a solvent. Thereafter, it is cooled to produce a thin polymer layer on the surface of the inert carrier. Such a polymer layer is formed easily on the inner side (side closer to the surface of the inert carrier), and on the outer side is difficult to crystallize. Next, by elevating the temperature continuously or stepwise, first, at a low temperature, the polymer is eluted from an amorphous part in the target polymer, that is, from a polymer having a high degree of short-chain branching. As the elution temperature rises, the one with a little branching degree is gradually eluted, and finally the linear part without branching is eluted to complete the measurement. The concentration of the elution component at each temperature is continuously detected, and the composition distribution of the polymer can be measured by the peak of the graph (elution curve) drawn by the elution amount and elution temperature.

  The ethylene-α-olefin copolymer preferably used as the polyolefin resin of the present invention exhibits the following physical properties.

Melt flow rate (MFR)
The MFR measured according to JIS-K7210 is 0.01 to 10 g / 10 min, preferably 0.1 to 5 g / 10 min. 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.

Density The density measured by JIS-K7112 is 0.880 to 0.930 g / cm ³ , preferably 0.880 to 0.920 g / cm ³ . 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.

Molecular weight distribution The molecular weight distribution (weight average molecular weight / number average molecular weight) determined by gel permeation chromatography (GPC) 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.

  The ethylene-vinyl acetate copolymer resin used in the present invention has a vinyl acetate content in the range of 10 to 25% by weight, preferably in the range of 12 to 20% by weight. 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, since the melting point of the resin is low, the film is slackened at the high temperature in summer during house extension, flutters due to wind and the like, and is easily broken due to rubbing with the house structure.

  In the present invention, by blending an ethylene / cyclic aminovinyl compound copolymer with a polyolefin-based resin, it is excellent in long-term weather resistance and bleed-out resistance, and the adhesion of the antifogging film is good and the film is peeled off. It is possible to obtain an agricultural film in which anti-fogging failure due to is difficult to occur. Compared with hindered amine weathering agents used for general agricultural films, the ethylene / cyclic aminovinyl compound copolymer not only provides an effect as a light stabilizer that significantly improves long-term weather resistance, but also prevents it. It plays the role of improving the adhesion to the surface of the coating including the cloudy coating.

The ethylene / cyclic aminovinyl compound copolymer that can be used in the present invention is a copolymer of ethylene (A) and a cyclic aminovinyl compound (B), or a copolymer of ethylene (A) and a vinyl compound of the following formula (3). Coalescence can be used. Since the ethylene / cyclic aminovinyl compound copolymer can be added in a large amount to change the surface properties (waterdrop contact angle, etc.) of the polyolefin film, it can be suitably used for the purpose of the present invention.

  In said formula (3), R1 and R2 represent a hydrogen atom or a methyl group each independently, and R3 represents a hydrogen atom or a C1-C4 alkyl group. Preferably, R1 and R2 are each a hydrogen atom or a methyl group, and R3 is a hydrogen atom.

The vinyl compound (B) represented by the formula (3) is known and can be synthesized by a known method, for example, a method described in JP-B-47-8539, JP-A-48-65180, or the like. it can.
Representative examples of the vinyl compound (B) represented by the formula (3) 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.
The presence of the cyclic aminovinyl compound (B) is confirmed as follows, as described in JP-A-4-80215. In 13C-NMR (for example, JNM-GSX270 Spectrometer manufactured by JEOL Ltd.), according to a known method (for example, Chemical Doujinshi "Electrical Analyzes (1)" pages 53 to 56 (1985)), Ethyl acrylate (see "Analytical bookstore," Polymer Analysis Handbook ", page 969 (1985)) and ethylene-hydroxyethyl acrylate copolymer (Eur. Poly. J. 25, 4, 411-418 (1989)) The 22.9 ppm peak in the TMS standard is attributed to the methylene group at the α-position from the branch point of the isolated vinyl compound (B), and the 35.7 ppm peak is two consecutive vinyls. It was attributed to the methylene group sandwiched between the branch points of the compound (B). Using these two signals, the proportion of the vinyl compound (B) present in isolation in the copolymer of ethylene (A) and vinyl compound (B) can be calculated by the following formula.

  The proportion of the vinyl compound (B) -derived structural unit derived from the vinyl compound (B) having a hindered amine group in the side chain estimated as described above is not continuous but is present in an isolated manner relative to the total amount of the vinyl compound (B) in the copolymer. It is preferably 83% or more. If the proportion of vinyl monomers having hindered amine groups in the side chain is less than 83% without two or more vinyl monomers having hindered amine groups in the side chain, the light stability is relatively high In some cases, the feature of having

The MFR (value measured according to JIS-K6760 (190 ° C., 2.16 kg load)) of the ethylene / cyclic aminovinyl compound copolymer is 0.1 to 200 g / 10 min, preferably 0.5 to 20 g / 10 minutes, more preferably 1-5 g / 10 minutes. When the MFR is less than the above range, the compatibility with the polyolefin resin is poor, and when blended, it causes visible defects in film applications such as fish eyes and boots. On the other hand, if the MFR exceeds the above range, even if the copolymer has a large molecular weight, bleeding or blooming due to diffusion loss occurs, or when blended with a polyolefin resin, the strength of the resulting resin composition may be reduced. Cause.

  Further, the ethylene / cyclic aminovinyl compound copolymer is expressed by a ratio of the weight average molecular weight to the number average molecular weight determined by preparing a calibration curve with monodisperse polystyrene using GPC. The value is preferably in the range of 3 to 120. A particularly preferred range is 5-20.

The ethylene / cyclic aminovinyl compound copolymer is produced by subjecting required monomers to copolymerization conditions, but can be produced by a high-pressure low-density polyethylene production apparatus. Usually produced by radical polymerization, the catalyst used is a free radical generator, such as dialkyl peroxides, diacyl peroxides, peroxyesters, ketone peroxides, peroxyketals, hydroperoxides, azo Compounds and the like are useful. As the polymerization apparatus, a continuous stirring tank reactor or a continuous tube reactor generally used in the high-pressure radical polymerization method of ethylene can be used. The polymerization pressure is about 1000 to 5000 kg / cm ² , and the polymerization temperature is about 100 to 400 ° C.

  In the present invention, the content of the ethylene / cyclic aminovinyl compound copolymer in the polyolefin resin composition is 2 to 10 parts by weight, preferably 2 to 8 parts by weight with respect to 100 parts by weight of the polyolefin resin. . If this content is less than the above range, the weather resistance is inferior because it is inferior, and if it exceeds the above range, it is not preferable in terms of economy.

  In the present invention, when the base film is a multilayer film, the ethylene / cyclic aminovinyl compound copolymer to be used is not necessarily contained in all layers of the multilayer film from the viewpoint of cost. It is sufficient that one layer is contained. Further, the ethylene / cyclic aminovinyl compound copolymer can be used in combination with one or more hindered amine weathering agents usually used for agriculture. Further, one or two or more hindered amine weathering agents which are usually used can be used for the layer not containing the ethylene / cyclic aminovinyl compound copolymer. For example, it can be contained in the innermost layer and the outermost layer (corresponding to the outer surface of the house when used as a film for house exterior), and the other layers can contain hindered amine light stabilizers that are usually blended for agriculture. .

  Moreover, in the polyolefin-type resin film used as a base film by this invention, the various additives normally used for a synthetic resin can be used together. These additives include, for example, ultraviolet absorbers, weathering agents, hindered amine compounds other than the ethylene / cyclic aminovinyl compound copolymer, infrared absorbers (heat retention agents), antifogging 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.

  Examples of hindered amine compounds that can be used in the present invention 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) Butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidylo Cycarbonyloxy) 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-tetra Azadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-tria / N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2,2,6,6-tetramethyl-4- Piperidyl) hexamethylenediamine / dibromoethane condensate.

  Examples of commercially available hindered amine compounds that can be used in the present invention and are usually used for agricultural purposes include TINUVIN 770, TINUVIN 780, TINUVIN 144, TINUVIN 622LD, TINUVIN NOR 371, CHIMASSORB 119FL, CHIMASSORB 944 (manufactured by Ciba Geigy Corp.), Sanol L 76 (Sankyo Co., Ltd.), MARK LA-63, MARK LA-68, MARK LA-68, MARK LA-62, MARK LA-67, MARK LA-57, LA-900, T-1167L (above, Asahi Denka) (Manufactured by Co., Ltd.), UV-3346, UV-3529, UV-3581, UV-3853 (above, manufactured by Cytec Corporation) and the like. These piperidine ring-containing hindered amine compounds are used alone or in combination of two or more.

  Content of the said piperidine ring containing hindered amine type compound is 0.001 to 5 weight% with respect to 100 weight% of thermoplastic resins, 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.

  From the viewpoint of cost, for example, when used in a multilayer film, the hindered amine compound used in the present invention does not necessarily need to be contained in all layers of the multilayer film, and may be contained in at least one layer. . For example, in the case of a multilayer film, the influence on the coating film extends from additives transferred to and transferred from other layers in addition to the additive added to the layer in contact with the coating film. Although a layer or an inner / outer layer is preferable, only an inner layer, only an intermediate layer, only an outer layer, or any combination thereof may be used.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 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-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2 2- (2'-hydroxyphenyl) such as (2'-hydroxy-3'.5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol ) Benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3 ′, 5′-ditertiarybutyl-4′-hydroxybenzoate, 2,4-ditertiaryamylphenyl-3 Benzoates such as', 5'-ditert-butyl-4'-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2- Substituted oxanilides such as ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate Cyanoacrylates such as methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [ (Hexyl) oxy] -phenol, triazines such as 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, and the like. can give. These ultraviolet absorbers are used alone or in combination of two or more.

Especially, a triazine type ultraviolet absorber can be preferably used from a viewpoint of the sustainability of an ultraviolet cut effect. In particular, when the triaryltriazine-type ultraviolet absorber is a triaryltriazine-type ultraviolet absorber described in the following general formula (2), the absorption wavelength is shorter than that of the benzotriazole-type ultraviolet absorber. This is very preferable because it does not affect not only the control effect but also the flower color development (particularly, inhibition of anthocyanin pigment expression) in the cultivation of flowers such as roses.

(Wherein R3 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
In the film used in the present invention, from the viewpoint of compatibility and the like, more preferably, R3 in the formula (2) is an octyl group, R4 to R7 are methyl groups, and R3 in the formula (2) is Examples thereof include a hexyl group, and R4 to R7 are hydrogen atoms.

  The content of the ultraviolet absorber is more than 0.001% by weight and less than 2% by weight, preferably 0.01 to 1% by weight, more preferably 0.01 to 0.8% by weight based on 100% by weight of the polyolefin resin. %. 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.

  When using the ultraviolet absorber represented by the general formula (2) in the present invention, from the viewpoint of cost, for example, when used for a multilayer film, it is not necessarily contained in all layers of the multilayer film, It is sufficient that at least one layer is contained. Moreover, the ultraviolet absorber shown by this General formula (2) can be used in combination with 1 type, or 2 or more types of other ultraviolet absorbers.

  The infrared absorbent (heat retention agent) that can be used in the present invention 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, Ca, Li 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 compound, lithium aluminum composite Hydroxides, aluminum / lithium / magnesium composite carbonate compounds, aluminum / lithium / magnesium composite silicate compounds, magnesium / aluminum Um silicon composite hydroxide, magnesium aluminum silicon composite sulfate compounds, magnesium aluminum silicon composite carbonate compound, a metal complex hydroxide salt containing more anions. These may be obtained by dehydrating crystal water.

  The infrared absorber (heat retention agent) may be a natural product or a synthetic product. The inorganic fine particles can be used without being limited by the crystal structure, crystal particle diameter, and the like.

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

  In addition, the infrared absorber (heat retention agent) has a surface of higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal salt such as alkali metal dodecylbenzenesulfonate, Those coated with fatty acid amides, higher fatty acid esters or waxes can also be used.

  The said infrared absorber (heat retention agent) can be used individually or in combination of 2 or more types. The average particle diameter is preferably in the range of 0.05 to 15 μm, more preferably 0.1 to 10 μm. If the average particle size of the infrared absorber (heat retention agent) is smaller than the above range, the dispersibility in the resin is poor and the appearance of the film (inorganic secondary agglomerates) is deteriorated and the film appearance is deteriorated. The powdering at the time is intense and the handling is inferior. On the other hand, if the average particle size of the infrared absorbing agent (heat insulating agent) is larger than the above range, the transparency is inferior or the extruder breaker screen is clogged, and the productivity is deteriorated.

  The content of the infrared absorber (heat retention agent) is preferably more than 0.1% by weight and less than 15% by weight, and more preferably 1 to 12% by weight with respect to 100% by weight of the polyolefin resin. When the content is 0.1% by weight or less, the effect of improving heat retention is low, and when the content is 15% by weight or more, there are problems such as a decrease in transparency.

  As metal species constituting the organic acid salt, basic organic acid salt and overbased organic acid salt of the metal used as the additive for the base film, Li, Na, K, Ca, Ba, Mg, Sr, Examples thereof include Zn, Cd, Sn, Cs, Al, and organic Sn. Examples of organic acids include carboxylic acids, organic phosphoric acids, and phenols. Examples of the carboxylic acids include acetic acid, propionic acid, butyric acid, Herbic acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid Acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptop Pionic acid, octyl mercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, Monovalent carboxylic acids such as ethylbenzoic acid, cumic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Divalent acids such as suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, etc. Carboxylic acid or monoester or monoamide compound thereof Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, and pyromellitic acid. Mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, etc., and the phenols Are phenol, cresol, xylenol, methylpropylphenol, methyl tert-octylphenol, ethylphenol, isopropylphenol, tert-butylphenol, n-butylphenol, diisobutylphenol, isoamylphenol, dia Milphenol, isohexylphenol, octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol, dodecylphenol, octadecylphenol, cyclohexylphenol, phenylphenolphenol, cresol, ethylphenol Cyclohexylphenol, nonylphenol, dodecylphenol, and the like.

  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], 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide] 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6- Tributylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4, 4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6- Tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3) -Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate 1,3,5-tris (3,5-ditert-butyl-4-hydroxylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) 2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9- Bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5. ] Undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], n-octadecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) ) Propionate, tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 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, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, monodecyl diphenyl phosphite, mono (dinonylphenyl) Bis (nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) penta Erythritol diphosphie Bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (C 12-15 mixed alkyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-) 5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 2,2′-methylenebis (4,6-ditert-butylphenyl) (octyl) phosphite , Tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene-di Phosphonites, 2,2-methylenebis (4,6-di -t- butyl phenyl) octyl phosphite, and the like.

  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.

  As the anti-blocking agent that can be used in the present invention, inorganic fine particles, organic fine particles and the like can be used. An inorganic filler containing at least one selected from Si, Mg, Al, Li, and Ca can be used as a constituent element component of the inorganic fine particles. Among these, diatomaceous earth, natural silica, synthetic silica, talc, mica, zeolite, and the like that can be usually used as an antiblocking agent can be suitably used. As the organic fine particles, for example, polymer beads mainly composed of a thermoplastic resin can be used. Among them, acrylate, methacrylate, styrene, nylon polymers and / or copolymers thereof can be preferably used.

  In addition, for the purpose of assisting the antifogging effect of the antifogging film of the present invention, a surfactant (including a fluorosurfactant) is added as long as it does not exert an antagonistic action with the fluorescent substance of the present invention. can do.

  Examples of the surfactant include polyhydric alcohol partial esters composed of polyhydric alcohols and higher fatty acids, including various known nonionic surfactants, anionic surfactants, and cationic surfactants. Of these, silicone-based surfactants and fluorine-based surfactants are suitable. 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-based 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.

  The above-mentioned fluorosurfactant is a surfactant in which a part or all of the surfactant is substituted with F instead of H bonded to C of the hydrophobic group of a normal surfactant, and particularly a perfluoroalkyl group or perfluoroalkenyl. A surfactant containing a group. The above various additives can be used alone or in combination of two or more. 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.

  The base film used in the present invention is formed by combining the above-described components with the fluorescent substance of the general formula (1) and the polyolefin-based resin, and can further contain the following optional components as necessary. Optional ingredients include other stabilizers, impact resistance improvers, crosslinking agents, fillers, foaming agents, antistatic agents, nucleating agents, plate-out preventing agents, surface treatment agents, flame retardants, other fluorescent agents, Examples include antifungal agents, bactericides, metal deactivators, mold release agents, pigments, processing aids, and the like.

  As a method of blending various additives into the base material used in the present invention, each required amount is weighed, and a blender such as a ribbon blender, a Banbury mixer, a Henschel mixer, a super mixer, a single or twin screw extruder, a roll, A kneader or other conventionally known blender or mixer 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.

  When the resin composition containing the fluorescent substance represented by the formula (1) is processed at 200 ° C. or higher, it is thermally decomposed, so that when it is formed into a base film of an agricultural polyolefin film, the strength of the film is reduced by foaming. , Transparency may be reduced. Therefore, the resin temperature is preferably 180 ° C. or lower, more preferably 160 ° C. or lower. For example, at a molding temperature of 160 ° C., appearance defects such as melt fracture may be a problem, but this can be avoided by appropriately selecting the resin composition.

  The polyolefin film for agricultural use of the present invention is characterized in that a layer made of an antifogging agent composition containing inorganic fine particles and / or a synthetic resin binder as a main component is formed on the base film. Examples of the layer made of the antifogging agent composition include an antifogging film described in JP-A-2001-89751, a type disclosed in JP-A-2005-96430 without a binder resin, and JP-A-2007-282625 and JP-A-2008. A multilayer antifogging film as described in -67645 can also be used preferably. Furthermore, a dry coating method called vapor deposition or effect fine particle deposit is also applicable.

  As the inorganic fine particles, metals, metal oxides, metal hydroxides, metal sulfates, metal carbonates, etc., metal composite hydroxides, etc., known ones can be used as long as they do not impair hydrophilicity to the film surface. I can do it.

  As the inorganic fine particles, an inorganic colloidal substance can be preferably used in the case of wet coating. As inorganic colloidal substances, inorganic aqueous colloidal particles such as silica, alumina, water-insoluble lithium silicate, zinc oxide, zirconium oxide, iron hydroxide, tin hydroxide, titanium oxide, antimony oxide, barium sulfate, zinc antimonate, Aqueous sols dispersed in water or hydrophilic media in various ways are mentioned. Of these, colloidal silica and colloidal alumina are preferably used, and these may be used alone or in combination. Of these, inorganic fine particles with strong photocatalytic action can be used in combination with other inorganic fine particles to reduce the substantial addition concentration, or by applying surface treatment within a range that does not impair hydrophilicity, to base materials and synthetic resin binders. It is necessary to reduce the influence of.

  The inorganic colloidal substance can be subjected to a surface treatment within a range that does not inhibit the imparting of hydrophilicity to the film surface in order to improve the adhesion between the inorganic colloidal sols during drying or between the inorganic colloidal sol and the synthetic resin binder. As a method for surface treatment on the colloidal silica surface, known methods can be used, and among them, a silane compound such as a silane coupling agent can be preferably used.

  Examples of the binder resin used for the synthetic resin binder in the present invention include acrylic resins, epoxy resins, urethane resins, polyester resins, and the like, from the compatibility with a base film made of a polyolefin resin, In particular, it is preferable to use an acrylic resin and / or a urethane resin, and more preferably (a) a hydrophilic acrylic resin, (c) a hydrophobic acrylic resin, which will be described later, (e) A hydrophobic acrylic resin and a polyurethane emulsion are preferred from the following characteristics.

  As the acrylic resin, (a) a hydrophilic acrylic resin, (b) a block copolymer containing a hydrophobic molecular chain block and a hydrophilic molecular chain block in one molecule, (c) Examples include those composed of hydrophobic acrylic resins. In particular, (a) is preferable in terms of early antifogging and wettability, but it tends to be washed away. Must be granted. On the other hand, (c) is excellent in water resistance and preferable in terms of antifogging durability, but the ratio of the binder resin and the inorganic colloidal substance is adjusted in order to suppress surface hydrophobicization by the hydrophobic acrylic resin. There is a need.

The hydrophilic acrylic resin (a) has a hydroxyl group-containing vinyl monomer component as a main component (preferably 60 wt% to 99.9 wt%, more preferably 65 wt% to 95 wt%), and an acid group. Examples thereof include a copolymer containing 0.1 to 30% by weight of a vinyl monomer component, a partially neutralized product 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- Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) An acrylate etc. are mention | raise | lifted. 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 terene, vinyl chloride, vinylidene chloride, vinyl oxide, (meth) acrylic acid esters, N, N-dimethylaminoethyl (meth) acrylamide, vinyl pyridine, and the like. In addition to these, a monomer containing a crosslinking site is copolymerized and an appropriate crosslinking agent is reacted at an appropriate crosslinking temperature, whereby the crosslinking density can be improved and the water resistance can be improved.

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- Butyl ester, acrylic acid-2-ethylhexyl ester, acrylic acid decyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid-n-propyl ester, methacrylic acid isopropyl ester, methacrylic acid-n-butyl ester, methacrylic acid- 2-ethylhexyl ester, methacrylic acid decyl ester, and the like. Generally, an alkyl alkyl group having 1 to 20 carbon atoms and / or a methyl group having 1 to 20 carbon atoms is used. Acrylic acid alkyl esters 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. In the case of a polymerization method in the presence of an emulsifier, these emulsifiers are used in the range of 0.1 to 10% by weight with respect to the total amount of charged monomers. It is preferable from the viewpoint of stability.

  Examples of the polymerization initiator preferably used for the production of the acrylic resin include persulfates such as ammonium persulfate and potassium persulfate; organic peroxides such as acetyl peroxide and benzoyl peroxide. 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 urethane-based resin that can be used in the present invention include polyether-based, polyester-based, and polycarbonate-based anionic polyurethane aqueous compositions and emulsions. Polycarbonate anionic polyurethane emulsion is preferable in terms of adhesion, water resistance and scratch resistance, and further increases the water resistance and scratch resistance of the antifogging coating, as well as the time until the antifogging property is developed and antifogging. A polycarbonate-based anionic polyurethane emulsion containing a silanol group is more preferable in terms of 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.

  An anionic surfactant, a cationic surfactant, a nonionic surfactant, and a polymeric surfactant, as long as the effect of the present invention is not impaired when the antifogging agent composition of the present invention is prepared. A surfactant such as can be added. In particular, when these surfactants are added to a base material, they may have an antagonistic action with a fluorescent substance. From the viewpoint of avoiding this, the antifogging property is imparted by forming a layer comprising an antifogging agent composition. It is preferable.

  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, sodium polyoxyethylene alkyl phenyl ether sulfate, etc. 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; pentaerythritol fatty acid esters such as dipentaerythritol monopalmitate; 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.

  By adding these surfactants, the binder resin and the inorganic colloid sol can be easily and quickly uniformly dispersed, and when used in combination with the inorganic colloid sol, hydrophilicity is imparted to the surface of the hydrophobic polyolefin resin film. Fulfills the function of 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 solid content of the resin.

  When preparing the anti-fogging agent composition according to the present invention, a crosslinking agent can be added. The crosslinking agent is particularly effective in crosslinking acrylic resins to improve the water resistance of the coating. Examples of the crosslinking agent include phenolic resins, amino resins, carbodiimide compounds, amine compounds, aziridine compounds, azo compounds, isocyanate compounds, epoxy compounds, silane compounds, etc., but particularly amine compounds. Aziridine compounds and epoxy compounds can be preferably used.

  Examples of amine compounds include aliphatic polyamines such as diethylenetriamine, triethylenepentamine and hexamethylenediamine; alicyclic amines such as 3,3′-dimethyl-4,4′-diaminocyclohexylmethane and isophoronediamine; 4-4 Aromatic amines such as' -diaminodihenylmethane and m-phenylenediamine are used. Examples of the aziridine compounds include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane-tri-β-aziridinylpropionate, tris [1- (2- Methyl) -aziridinyl] phosphine oxide, hexa [1- (2-methyl) -aziridinyl] triphosphatriazine and the like are used.

  Epoxy compounds include reaction products of bisphenol A or bisphenol F and epichlorohydrin, epoxidized novolak resins, epichlorohydrin and aliphatics produced by the reaction of a resin reaction product of phenol (or substituted phenol) and formaldehyde with epichlorohydrin. Resin-like reaction products produced from polyhydric alcohols such as glycerol, 1,4-butanediol, poly (oxypropylene) glycol or similar polyhydric alcohol components, and resins obtained by epoxidation using peracetic acid are used. The Epoxy compounds can be used in combination with tertiary amines or quaternary ammonium salts as catalysts. These crosslinking agents can be used in an amount of 0.1 to 30% by weight based on the acrylic resin solid content.

  A liquid dispersion medium can be mix | blended with the anti-fogging agent composition in 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.

  In the antifogging agent composition of the present invention, pigments, pigment dispersants, fillers, anti-settling agents, anti-sagging agents, antifoaming agents, leveling agents, anti-repelling agents, and adhesiveness that can be incorporated into ordinary paints An improver, an antiseptic, an algae, a fungicide, a deodorant, an ultraviolet absorber, a weathering agent, a plasticizer, a film-forming aid, a thickener, a coupling agent, and other various additives can be blended. The addition amount is not particularly limited, and may be appropriately selected within a range that does not affect the effects of the present invention.

  Although the mixing method of the antifogging agent composition in this invention is not specifically limited, It is preferable to mix uniformly and the temperature at the time of mixing | blending and the mixing method can select a suitable method suitably.

  Moreover, when the adhesiveness of a base film and the layer which consists of an antifogging agent composition is not enough, you may surface-treat to a base film. Examples of the treatment method applied to the surface of the substrate film 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.

  In order to form a layer composed of the antifogging agent composition on the outermost surface of the base film in the present invention, a known wet or dry coating method can be arbitrarily selected. Wet coating with simple construction equipment is preferably used. In the case of wet coating, generally the solution or dispersion of the anti-fogging agent composition is applied to the doctor blade coating method, roll coating method, dip coating method, spray coating method, rod coating method, bar coating method, knife coating method, brush coating, respectively. A known coating method such as a method may be adopted 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, it is usually 50 to 200 ° C., preferably 70 to 180 ° C., more preferably 70 to What is necessary is just to dry in the temperature range of 150 degreeC. When the drying temperature is higher than 200 ° C., even when the drying time is short, the fluorescent material in the base material may be thermally deteriorated, which may cause deformation problems such as melting of the base film and heat shrinkage. 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.

In the case of wet drying, the coating amount of the antifogging composition is not particularly limited, but is preferably 0.01 to 10 g / m ² , more preferably 0.1 as the coating amount per unit area at the time of drying. ˜5 g / m ² . Below this range, it is difficult to obtain good antifogging properties, and exceeding this range causes a decrease in transparency due to whitening, which is not preferable.

  The thickness of the layer composed of the antifogging agent composition in the case of wet drying (also referred to as “antifogging coating”) may be selected based on 1/10 or less of the base film, but is not necessarily limited to this range. It is not something. If the total thickness of the anti-fogging coating is greater than 1/10 of the base film, the base film and the coating have a difference in flexibility, causing phenomena such as peeling of the coating from the base film. This is not preferable because a phenomenon occurs in which the coating film is cracked and the strength of the base film is lowered.

  The agricultural polyolefin-based film of the present invention can form other coatings in addition to the antifogging coating. For example, an antifogging film may be formed on the inner surface of the house and a dustproof film may be formed on the outer surface of the house. In that case, the anti-blocking effect may be further improved by the dust-proof coating film.

  About the thickness of the polyolefin film for agriculture 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 it is less than this range, there is a problem in strength, and if it exceeds this range, molding is difficult and there is a problem in stretch workability.

  The agricultural polyolefin film of the present invention may be either a single layer or a multilayer film. In the case of a multilayer film, 3 to 5 layers are easy to balance each layer. 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.

  When the polyolefin film for agriculture according to the present invention is actually used, it is preferably stretched so that the side provided with the antifogging coating is inside the house or tunnel.

  In the present invention, the crop cultivation material is a film itself obtained by molding a resin composition composed of at least a polyolefin resin and a fluorescent material as a raw material, and a long film obtained by cutting the film In addition, woven or knitted fabrics made from flat yarns, monofilaments, and / or composite monofilaments, etc., obtained by further processing the film, are included.

  The production method of the film or material used to produce the crop cultivation material of the present invention is not particularly limited, and extrusion molding, injection molding, compression molding, etc. can be applied, and particularly extrusion molding. Are preferably used. Examples of the woven / knitted fabric include a net, but are not particularly limited. The crop cultivation material in the present invention can be produced by, for example, the method described in JP-A-2007-135583.

  In the present invention, the crop cultivation material is obtained by cutting a film obtained by molding a resin composition composed of at least a thermoplastic resin and a fluorescent material represented by the formula (1) as a raw material. However, as the film, it is preferable to use a film obtained by molding the resin composition containing the fluorescent material at a resin temperature of preferably 180 ° C. or lower, more preferably 160 ° C. or lower. Good. Thereby, generation | occurrence | production of foaming can be prevented at the time of film shaping | molding, the strength reduction of a film by a foaming, and transparency fall can be avoided, As a result, the crop cultivation material without a strength reduction can be obtained.

  Plants that can use the polyolefin film for agriculture and crop cultivation materials of the present invention include long-day plants (plants that react to long days to regulate flower bud formation) and short-day plants (react on short days). Thus, the present invention can be applied without particular limitation to a plant that regulates flower bud formation) and a neutral plant (a plant that does not respond to the photoperiod). Specific examples include flower garden plants, fruit vegetables, fruit trees, and cereals. Examples include orchids such as phalaenopsis, cymbidium, and dendrobium, cacti, roses, carnations, gerberas, gypsophila, lilies, and starches. Flowers for cut flowers, and flowers for pot flowers such as pansy, primula, begonia, petunia, cyclamen; fruit and vegetables such as tomato, cucumber, melon, strawberry, pepper; fruit trees such as pear, apple, grape And can be applied to cereals such as corn and wheat. In particular, in order to make the most of the effects of the present invention, a plant with a slow flower bud formation, a plant with a small number of flower bud formation in a natural state, or a plant that needs special seedlings more than the normal state is selected. It can be considered as a target.

  The method of cultivating the target plant is not particularly limited, and a method of planting and cultivating what has been germinated and raised using a tray or pot filled with cultivated soil, after germination on a sponge cube, The cultivation method according to the kind of plant and the purpose of cultivation, such as a method of hydroponics and a method of aseptically culturing and raising seedlings on agar containing nutrients, can be used.

  Further, suitable plants that can use the polyolefin film for agricultural use and the material for cultivating crops of the present invention are plants belonging to the family Rosaceae, in particular, the plant belonging to the subfamily Rosaceae, and specifically, roses, Hermanus, Onishimotsuke. , Bear strawberry, white yamabuki, yamabuki, strawberry, burdock, and kimimushiro, particularly suitable for cultivation of roses and strawberries.

  The polyolefin film for agriculture and the crop cultivation material of the present invention can be used effectively in cut rose cultivation and strawberry cultivation, more preferably in the above-described cultivation by the rose arching method.

  As a cultivation method by the rose arching method, there are a method described in JP-A-3-191716, JP-A-4-330231, JP-A-4-341123, and JP-A-7-39356. The polyolefin film for agriculture and the material for cultivating crops of the invention are suitably used for a cultivation method by a known rose arching method containing them.

  For example, take only the buds of the branches that initially grew in the early stages of cultivation, and the branches were artificially bent near the stock to maintain the lodging state, and the basal shoots generated from the vicinity of the stock were grown as branches. Cut and flower from the base without the leaves of the branches, and after the first flowering, grow the basal shoots generated from the bases without the leaves of all branches that are not flowered and cut from the base without the leaves of the branches When performing the method of cultivating roses by the arching method in which flowering is repeated, the agricultural polyolefin film of the present invention can be used as a lining or an outer film in a greenhouse for horticulture.

  The polyolefin film for agriculture of the present invention has very good antifogging property on the inner layer side of the house, while preventing the occurrence of diseases caused by the deterioration of cultivation due to insufficient light quantity due to light scattering by water droplets and the drop of water droplets, Agricultural materials that can achieve a high cropping effect, and when combined with a specific UV absorber, a high cropping improvement effect can be obtained for a long time without affecting the rose color. Very preferred. The agricultural material of the present invention can be suitably used as agricultural films and nets for house, tunnel, mulching, bag hanging and the like. The polyolefin film for agriculture of the present invention can be used for both outer and inner linings. Moreover, the suitable example which uses the polyolefin-type film for agriculture of this invention is shown in FIG. In addition, since the polyolefin film for agriculture of the present invention has a function of wavelength conversion, when used as a film for an outer layer, depending on the color of the cultivated crop, it may look different in appearance and color. If the film is still stretched, it may be difficult to judge the harvesting time, but if it is used as an outer covering, it can take in more sunlight, so that it can take in more red light.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, a reference example, and a comparative example, this invention is not limited to these at all.

(1) Evaluation of fluorescent substance A polyolefin-based three-layer film (inner layer / intermediate layer / outer layer thickness = 1/3/1, total thickness: 150 μm) having the following composition is prepared by three-layer inflation molding. Prior to this test, a three-layer inflation molding test was conducted for 150 ° C. and 200 ° C. processing temperatures (set temperatures of the extruder and the die). Confirmed that it occurred. Therefore, in this test, the molding temperature was set to 160 ° C. and the extruder temperature was set to 150 ° C.

  The main composition of the film was as follows. Although not specifically described, commercially available additives (additives such as anti-blocking agents and antioxidants) necessary for constituting agricultural films were used in usual amounts.

House inner and outer layers: Metallocene PE = ethylene / α-olefin copolymer produced with metallocene catalyst (MFR: 2 g / 10 min, density: 0.912)
House intermediate layer: EVA = ethylene-vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 2 g / 10 min)
Here, the following were used as the fluorescent substance.

Reference Example 1: SMART LIGHT RL1000 (manufactured by Ciba) (compound in which R1 = R2 = methyl group in formula (1)) 1.67% in the intermediate layer
Comparative Example 1: TIOPAL OB (Ciba) 1.67% in the intermediate layer
Comparative Example 2: Lumogen F Red 305 (manufactured by BASF) 0.0167% in the intermediate layer (Because it was incompatible with polyolefin resin, it was used in a reduced amount.)
Comparative Example 3: SX-103 (manufactured by Sinloihi) 1.67% in the intermediate layer

  FIG. 1 shows the initial total light transmittance of the polyolefin-based multilayer films of Reference Example 1 and Comparative Examples 1 to 3 thus obtained, and FIG. 2 shows the total light transmittance after a load test (90 hours). The total light transmittance was measured with a spectrophotometer (manufactured by Hitachi, Ltd., U3500 type). The load 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 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 each stated time in a 1 hour cycle without irradiation.

  Here, FIG. 1 shows that the films of Reference Example 1 and Comparative Examples 1 to 3 have absorption at wavelengths near 350 nm to 600 nm, and this indicates that light in the green region from the ultraviolet region has been absorbed. In addition, although the apparatus which measured the total light transmittance is a spectrophotometer of the type which scans a wavelength, since light emission cannot be measured, it can be considered that the light emission energy is large that absorption energy is large. From FIG. 1, it can be understood that the films of Reference Example 1 and Comparative Example 1 have a large absorption energy in the wavelength region of 350 nm to 600 nm, and thus the light emission at 600 nm or more (red region) is large.

  In order to confirm this point, the film of Reference Example 1 and the film without the addition of the fluorescent substance (Comparative Example 4: the same as the resin composition described above except that no fluorescent substance is added) are used. A test was conducted to examine wavelength conversion. The test measured the illuminance converted into the value for every 1 nm using the spectroradiometer "MS-720" by Hidehiro Seiki Co., Ltd. In addition, as a test method, a climatic condition in which the illuminance of sunlight was difficult to change in a short time was selected, and the illuminance was measured by covering the entire light receiving portion with a film. The result is shown in FIG. From FIG. 3, in the film of Reference Example 1, the absorption energy is larger than that in Comparative Example 4 at a wavelength in the vicinity of 350 nm to 600 nm, and the absorption energy is small at a wavelength in the vicinity of 600 nm to 700 nm. This indicates that the film of Reference Example 1 absorbs ultraviolet to green light and converts it into red light.

  Moreover, according to FIG. 1 and FIG. 2, in Comparative Example 1, the absorption energy at 350 nm to 600 nm is remarkably reduced, whereas the absorption energy in the wavelength region of the film of Reference Example 1 is almost reduced. Not done. From this result, the film of Reference Example 1 absorbs light having a wavelength of 350 nm to 600 nm after the load test, converts it to light in the vicinity of 600 nm to 700 nm, and emits light efficiently. From the above, it can be seen that the fluorescent material used in the present invention is superior in desired wavelength conversion performance and stability compared to other fluorescent materials.

(2) Evaluation of antagonistic action of antifogging agent In order to examine the antagonistic action of the fluorescent substance and the antifogging agent and its avoidance by forming the antifogging film, a polyolefin-based multilayer film having the following constitution was prepared. In addition, the commercially available thing was normally used for the other additive (additives, such as an antiblocking agent and antioxidant) required in order to usually comprise an agricultural film.

Resin composition House inner layer: EVA = ethylene / vinyl acetate copolymer (vinyl acetate content 5 wt%, MFR 2.3 g / 10 min)
House outer layer: Metallocene PE = ethylene / α-olefin copolymer produced with metallocene catalyst (MFR: 2 g / 10 min, density 0.912)
House intermediate layer: EVA = ethylene-vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 2 g / 10 min)
Main additive Fluorescent substance: SMART LIGHT RL1000 1.67% added in the intermediate layer Light stabilizer: tinuvin NOR 371 FF 0.4% added in the intermediate layer Ethylene / cyclic aminovinyl compound (XJ100H manufactured by Nippon Polyethylene Co., Ltd.) ): 8% added to the inner layer and outer layer respectively UV absorber: 0.09% added to the tinuvin 1577 ED intermediate layer Antifogging agent: 0.5 mol PO adduct of sorbitan palmitate ester In the inner layer and intermediate layer, respectively 1.5% added Diglycerol distearate / monoglycerol monostearate: 0.5% added to the inner layer

  Based on the above composition, the following three types of films were prepared.

Example 1: Fluorescent substance added, anti-fogging coating, no anti-fogging agent added Comparative Example 5: fluorescent material added, no anti-fogging coating, anti-fogging agent added Comparative Example 6: fluorescent material added, anti-fogging With anti-fogging coating and without addition of anti-fogging agent The anti-fogging coating was formed as follows.

Formation of anti-fogging film (anti-fogging film coating type)
Formulation composition of antifogging agent composition 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: Aziridine compound manufactured by Mutual Yakugyo Co., Ltd. The antifogging composition was applied to the surface of the base film 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 film. The thickness of the coating film of each obtained film was about 1 μm.

  The result of having measured the total light transmittance about said film is shown in FIG. From this figure, it can be seen that the film of Example 1 has sufficient absorbed energy while the absorbed energy at 400 to 500 nm is lowered in Comparative Example 5. Therefore, by forming an antifogging film on the base film containing the fluorescent substance in the present invention, the film is provided with excellent antifogging properties while avoiding the antagonistic action due to the addition of the antifogging agent to the base film. I understand what I can do.

(3) Evaluation of effect by addition of ultraviolet absorber The following samples were prepared.

0.4% triaryltriazine type UV absorber (tinuvin 1577 ED in the general formula (2), R3 is a hexyl group and R4-R7 represents a hydrogen atom) and another triaryltriazine type UV absorber in the intermediate layer (An antifogging property of the above (2) is added to the multilayer film having the same configuration as that of Reference Example 1 except that 0.2% of UV1164 in the general formula (2) is added in which R3 represents an octyl group and R4-R7 represents a methyl group). Film on which a film was formed (Example 2)
A film in which an antifogging film is formed on the film of Reference Example 1 (Example 3)

  With respect to the above film, the initial total light transmittance and the total light transmittance after a load test (250 hours) were measured. The load test was performed according to the test method performed in (1) (Evaluation of fluorescent substance). The results for the film of Example 3 are shown in FIG. 5, and the results for the film of Example 2 are shown in FIG. From FIG. 5, it can be seen that the absorption in the wavelength region of 350 to 600 nm after the load test (250 hours) decreases to some extent when no ultraviolet absorber is added. In contrast, FIG. 6 shows that the absorption in the wavelength range of 350 to 600 nm after the load test (250 hours) decreases only slightly. From these results, it can be seen that better wavelength conversion performance can be maintained even after a load test by combining a specific fluorescent material and a specific ultraviolet absorber (triaryltriazine type ultraviolet absorber).

(4) Cultivation test When a film containing a polyolefin-based agricultural film of the present invention and a fluorescent material but not forming an antifogging film is used as a wavelength conversion film for sunlight as a house lining film (FIG. 8), And commercially available red LED 1 (manufactured by Kyosemi Corporation: KED661M53 (gallium, aluminum, arsenic), emission peak: 660 nm, emission output (driving current 20 mA): 3 mW)), and commercially available red LED 2 (manufactured by Showa Denko KK) : HRP-350F (aluminum / gallium / indium / phosphorus), emission peak: 660 nm, emission output (drive current 20 mA): 11 mW)), fluorescent lamp treatment, no treatment (no lining film, LED, no fluorescent lamp) A rose arching cultivation test was conducted as follows.

Cultivation test method Test variety: Little Marvel (3-year strain)
Treatment method (1) The treatment time was 15 hours from 17:00 to 8:00 on the next day in any section.

(2) The processing time is from September 28, 2009 to November 15, 2009.

(3) The fluorescent lamp was irradiated with a lamp from a light source at a distance of 10 cm from the light source.

(4) For each light emitting diode, 10 light emitting diode chips were mounted per package (light emitting unit), and one package was disposed on a 4 cm wide, 120 cm long aluminum substrate at intervals of 5 cm in the length direction. This produced the LED panel which mounted about 240 light emitting diode chips in total.
(5) Each of the above LED panels was placed and irradiated on the part of the stock and the part where the leaves of the branch bent from the stock were crowded (an assimilation branch). The distance from the light source to the stock or leaf was 10 cm. The photon flux density at the irradiated portion of each light emitting diode was as follows.
Commercially available red LED 1: 40-50 μmol · m ⁻² · s ⁻¹
Commercially available red LED ² : 120 to 150 μmol · m ⁻² · s ⁻¹
(6) Regarding the treatment of the fluorescent lamp, in order to prevent the influence on the neighboring, it was partitioned with a foam plate in the center of the bench. FIG. 7 is a schematic diagram showing a state in which a rose bedside and an assimilation branch are irradiated. Moreover, when using a wavelength conversion film, the coating-type agricultural polyolefin film which does not mix | blend an ultraviolet absorber is spread as an outer film in a house, The wavelength conversion film of this invention (film of Example 2), It was installed in a normal lining curtain winding device and used as a lining film. A schematic diagram thereof is shown in FIG. For comparison, a test was also conducted on the case where the multilayer film of Reference Example 1 (film without an antifogging coating) was used as the lining film.

Outline of cultivation (1) Planting: April 24, 2009 (2) Cultivation density: 6 plants were planted per rock wool mat of 910 mm × 200 mm × 75 mm, and the mats were arranged in two rows on a 60 cm wide bench.

(3) Nutrient solution management: EC 0.8 to 1.5 ds / m
Number of times of liquid supply 11 times / day (4) Temperature control: Ventilation at 25 ° C, minimum temperature 18 ° C
(5) District system: Each strain has 12 strains, no repeats, and cut flower surveys targeted 5 strains.

  As shown in the table above, when using the film of Example 2, while preventing the deterioration of cultivatability due to insufficient light quantity due to light scattering by water droplets, the antifogging property on the inner side of the house is very good. High cultivatability improvement effect was able to be obtained. On the other hand, when the film of Reference Example 1 (without anti-fogging coating) is used, water droplets adhere to the inner layer side of the house and light scattering occurs, so the amount of light is insufficient and the expected wavelength conversion effect cannot be obtained. The cultivation ability was not greatly improved.

(5) Effect of addition of triaryltriazine type ultraviolet absorber As shown in the test of (3) above, the addition of an ultraviolet absorber is beneficial for improving the life of the fluorescent substance. This is because ultraviolet rays that cause deterioration of the fluorescent material can be absorbed. On the other hand, ultraviolet rays are required to some extent in order to keep the flower color in cultivation of roses and the like. Therefore, the type of UV absorber and the effect on rose flower color were investigated.

  The following film samples were prepared and used for a film for house exterior, and a red rose cultivation test was conducted.

(Example 5)
Transmission type three-layer polyolefin film (150 μm thickness): No UV agent added (Example 6)
Partial UV cut three-layer polyolefin film (150 μm thickness): Add 0.06% tinuvin 326 to the intermediate layer (benzotriazole type UV absorber)
(Example 7)
360 nm or less UV cut three-layer polyolefin film (150 μm thickness): 0.4% tinuvi 1577ED added to the intermediate layer and 0.2% UV 1164 added to the intermediate layer (both triaryltriazine type UV absorbers)
(Example 8)
380 nm or less UV-cut three-layer polyolefin film (150 μm thickness): tinuvin 326 is added in an intermediate layer of 0.9% (benzotriazole type UV absorber)
In all the films of Examples 5 to 8, 1.67% of a fluorescent material (SMART LIGHT RL1000) was added to the intermediate layer. Moreover, the main structures of these films are as follows, and other commercially available additives (anti-blocking agents, antioxidants, etc.) necessary for constituting agricultural films were used. Moreover, in any film of Examples 5-8, the antifogging film was formed in the way described in said (2) (evaluation of the antagonistic action of an antifogging agent).

House inner and outer layers: Metallocene PE = ethylene / α-olefin copolymer produced with metallocene catalyst (MFR: 2 g / 10 min, density: 0.912)
House intermediate layer: EVA = ethylene-vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 2 g / 10 min)

The test results are shown in the following table.

  From the above results, it is shown that the addition to a specific ultraviolet absorber (triaryltriazine type ultraviolet absorber) can avoid the inhibition of rose flower color (anthocyanin pigment expression).

  The polyolefin film for agriculture of the present invention has very good antifogging property on the inner layer side of the house, while preventing the occurrence of diseases caused by the deterioration of cultivation due to insufficient light quantity due to light scattering by water droplets and the drop of water droplets, Agricultural materials that can achieve a high cropping effect, and when combined with a specific UV absorber, a high cropping improvement effect can be obtained for a long time without affecting the rose color. Very preferred. The agricultural material of the present invention can be suitably used as agricultural films and nets for house, tunnel, mulching, bag hanging and the like.

Claims (12)

Antifogging agent composition comprising inorganic fine particles and / or synthetic resin binder as main component on base film made of polyolefin resin composition containing 0.1 to 5% by weight of fluorescent substance represented by formula (1) A polyolefin film for agriculture, comprising a layer made of a product.

(In formula, R1-R2 represents a hydrogen atom or a C1-C10 alkyl group each independently.)   The agricultural polyolefin-type film of Claim 1 whose R1, R2 in Formula (1) is a methyl group.   The agricultural polyolefin film according to claim 1 or 2, wherein the resin composition contains at least one triaryltriazine-type ultraviolet absorber. 4. The agricultural polyolefin-based film according to claim 3, wherein the triaryltriazine type ultraviolet absorber is a triaryltriazine type ultraviolet absorber represented by the following general formula (2).

(Wherein R3 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)   The agricultural polyolefin-type film of Claim 4 whose R3 in Formula (2) is a hexyl group, and R4-R7 is a hydrogen atom.   The agricultural polyolefin-type film of Claim 4 whose R3 in Formula (2) is an octyl group, and R4-R7 is a methyl group.   The triaryltriazine type ultraviolet absorber represented by the formula (2) is contained in an amount of more than 0.01% and less than 2.00% based on the weight of the total polyolefin resin in the base film. The agricultural polyolefin-type film as described in any one of Claims 3-6.   A cultivation method characterized by using the polyolefin film for agriculture according to any one of claims 1 to 7 as a lining or an outside film in a greenhouse for horticulture in cultivation of roses.   The cultivation method of the Rosaceae takes only the buds of the branches that grew first in the early stages of the cultivation, and the branches are bent artificially near the stock to maintain the lodging state. After the first flowering, the basal shoots generated from the bases without leaves of all branches that are not flowered are grown as branches and the leaves of the branches are grown. The cultivation method according to claim 8, wherein the cultivation method is an arching method in which cutting and flowering is repeated from a base that is not attached.   A woven or knitted fabric woven using the same or different materials selected from the films, flat yarns, monofilaments and their secondary processed products, each containing the fluorescent material according to claim 1 and made of a thermoplastic resin. A crop cultivation material characterized by   The material for cultivating crops according to claim 10, wherein the woven or knitted fabric is a net, and the porosity of the net is 70 to 10%.   The material for cultivating crops according to claim 11, wherein a content ratio of the fluorescent material to the thermoplastic resin is 0.001 to 5% by weight.

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