201224020 六、發明說明： 【發明所屬之技術領均^】 本發明係有關植物栽 栽培用溥膜之適用薄膜、其製造 方法及使用其之植物栽 ^ a ^ ^ . 。方法。更詳細係有關使用聚乙 烯醇與羧基可被中和之取#灿 法及使用其之植物栽培；；酸所形成之薄膜、其製造方 【先前技術】 在植物的培養液曲丄 裁培中，係提出有藉由在培養液與 植物體之間配置薄膜* ^ Αι ^ Λ ^ 犋來抑制培養液腐壞的植物栽培方法 (參照專利文獻1)。對哕 対》亥4膜而言，重要的是使養分穿透 ，而作為薄膜材料，佐 係鐽出有聚乙烯醇、玻璃紙 (cellophane)、乙酸鑰雉本 , 吸纖維素、硝酸纖維素、乙基纖維素、 聚酯等親水性材料。麸 ‘、、、而’透過上述栽培方法來栽培植 物之際，單純使用，μμ # Ab , 種親水性材料時仍存有細菌等通過 根所產生的貫穿部分， 刀 移動至培養液而使得培養液腐壞 之虞。 仲作為：制根的貫穿之方法係思及提高薄膜強度，惟 僅单純提高薄膜強_ k I、 、強度仍有養分穿透性等、強度以外的其 他）·生質劣化的問題。舉例而言，作為提高聚乙稀醇薄膜 強度之方法係有交聯的導人’然如專利文獻2及3所記戴 ’作為乂聯劑係使用聚丙烯酸、其部分中和物，以高溫 、呈長時間熱處理的薄膜'其強度雖得以提升，但養分穿透 性極差’而不適用為植物栽培用薄膜。此外’關於導入 父聯的方法除專利文獻2及3以外，亦已知有包含在聚 乙稀醇的存在下將甲基丙烯酸聚合所得之組成物的薄犋 201224020 (參照專利文獻4)、由包含特定聚乙烯醇及特定含有羧基 之聚合物的組成物所形成的薄膜（參照專利文獻5)，惟此 等薄膜在薄膜強度方面仍有待進一步的改良。因此，便 要求一種薄膜強度高且養分穿透性亦優良的薄膜。 [先前技術文獻] [專利文獻] [專利文獻1]曰本特開2008-61 503號公報 [專利文獻2]曰本特開平6-22022 1號公報 [專利文獻3]曰本特開平7-102083號公報 [專利文獻4]美國專利第2 1 6925 0號說明書 [專利文獻5]日本特開2007-199248號公報 【發明内容】 [發明所欲解決之課題] 本發明之目的在於提供一種薄膜強度高、可抑制根 的貫穿且養分穿透性亦優良而使植物體得以良好地生長 之植物栽培用薄膜的適用薄膜、其製造方法及使用其之 植物栽培方法。 [用以解決課題之手段] 本發明人等為達上述目的而致力進行多次研究的結 果發現，以65 : 3 5〜95 : 5的質量比使用聚乙烯酵與羧基 可被中和之聚羧酸形成薄膜，並對其在特定條件下實施 熱處理藉以將其軟化點調整成75〜9(rc，則可製成薄膜強 度n、可抑制根的貫穿且養分穿透性亦優良而使植物體 得以良好地生長的薄膜。本發明人等便基於此等所得之 知識’進—步進行多次研究而完成本發明。 201224020 即，本發明係有關· [1]一種薄膜，其係以65 : 35〜95 ·· 5的質量比使用聚乙烯 醇（以下有將「聚乙烯醇」簡稱為「PVA」）與叛基可被中 和之聚叛酸（以下有將「叛基可被中和之聚缓酸」僅簡稱 為「聚羧酸」）而形成，且軟化點為75〜90。(：； [2]如[1]之薄膜’其中前述聚繞酸為聚（曱基）丙烯酸系聚 合物及聚（曱基）丙烯酸系聚合物之中和物的至少一者； [3]如[1]或[2]之薄膜’其貫穿抵抗力在換算成厚度6〇μιη 時的値之際為17.0Ν以上·，該貫穿抵抗力係以浸潰於2〇t 的水中i分鐘後，穿刺日本工業規格A55〇8: 2〇〇9所規定 的粗圓鐵釘（CN65)之際的最大荷重來測定； [4] 如[1]至[3]中任一項之薄膜，盆Λ ，、馬植物栽培用薄膜； [5] —種薄膜之製造方法，其包含 八匕3對由原液製成之薄膜以 13 0〜170°C之範圍内的溫度實摊埶# \ I她熟處理6〜丨4分鐘之步驟 ，其中該原液係以65 : 35〜95 : 5的皙县u·人一 幾酸； 5的質篁比含有PVA與聚 [6] 如[5]之製造方法，前述 人物芨田甘、 硬敁馮聚（甲基）丙烯酸系4 σ物及聚(甲基)丙烯酸系聚合物之中和 [7] 如[5]或[6]之製造方法，盆 ^者， 方法； /、為植物栽培用薄膜之製史 其係以使植物與[4]之薄膜直接接 [8]一種植物裁培方法 觸的方式來裁培植物 [發明之效果] 貫穿且養分 可提供一種薄膜強度高 亦優良而使植物體得以 、可抑制根的 良好地生長之 201224020 植物栽培用薄膜的適用薄膜、其製造方法及使用其之植 物栽培方法。 【實施方式】 [實施發明之形態] 以下對本發明詳細進行說明。 作為構成本發明中所使用之PVA，可使用將聚乙稀 醋皂化所製得者；該聚乙烯酯係將乙酸乙烯酯、甲酸乙 稀醋、丙酸乙烯酯、丁酸乙烯酯、三甲基乙酸乙烯醋、 二甲基丙酸乙烯酯（vinyl versatate)、月桂酸乙烯酯、硬 月曰酸乙烯酯、安息香酸乙烯酯、乙酸異丙烯酯等乙烯酯 的1種或2種以上聚合而得。上述乙烯酯當中，由pVA之 製造容易性、獲得容易性、成本等觀點言之，較佳為乙 酸乙烯酯。 上述聚乙烯酯較佳為僅使用丨種或2種以上乙烯酯作 為單體所製得者’更佳為僅使用丨種乙烯酯作為單體所製 得者，只要處於未損及本發明之效果的範圍内，亦可為工 種或2種以上乙烯酯、及可與其共聚合的其他單體所形成 的共聚物。 作為可與上述乙烯酯共聚合的其他單體，可例舉如 乙稀、丙稀、1-丁烯、異丁烯等碳數2〜3〇之〇1_烯烴；（甲 基）丙烯酸甲醋、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙 酯、（曱基）丙烯酸異丙酯、（曱基）丙烯酸正丁酯、（甲基） 丙稀酸異丁酯、（甲基）丙烯酸三級丁酯、（曱基）丙稀酸2· 乙基己酯、（曱基）丙烯酸十二酯、（曱基）丙烯酸十八酯等 (甲基）丙烯酸酯；（曱基）丙烯醯胺、N_甲基（曱基）丙烯醯 201224020 胺、N-乙基（曱基）丙烯醯胺、Ν,Ν-二甲基（曱基）丙烯醯胺 、二丙酮（甲基）丙烯醯胺、（曱基）丙烯醯胺丙烷磺酸或其 鹽 '(甲基）丙烯醯胺丙基二曱胺或其鹽、Ν-羥曱基（甲基 )丙烯醯胺或其衍生物等（曱基）丙烯醯胺衍生物；Ν -乙烯 基甲醯胺、Ν-乙烯基乙醯胺、Ν-乙烯基吡咯啶酮等Ν-乙 烯基醯胺；甲基乙烯醚、乙基乙烯醚、正丙基乙烯醚、 異丙基乙稀醚、正丁基乙烯趟、異丁基乙稀醚、三級丁 基乙烯醚、十二烷基乙烯醚、硬脂醯乙烯醚等乙烯醚；（ 甲基）丙烯腈等乙烯氰化物；氣乙烯、二氣亞乙烯、氟乙 烯、二氟亞乙烯等乙烯齒化物；乙酸烯丙酯、烯丙基氣 等烯丙基化合物；乙烯基三甲氧基矽烷等乙烯基矽基化 合物；不飽和磺酸等。上述聚乙烯酯可具有前述其他單 體的1種或2種以上所衍生的結構單位。 基於構成聚乙烯酯之整體結構單位的莫耳數，前述 其他單體所衍生的結構單位在上述聚乙烯酯中所占的比 例較佳為1 5莫耳％以下’更佳為丨〇莫耳％以下再更佳為 5莫耳％以下。 特別是當前述其他單體為如不飽和磺酸等可能促進 所得之PVA的水溶性的單體時，將所得之薄膜.用作植物 裁培用薄膜之際等，為防止薄膜溶解，則基於構成聚乙 稀醋之整體結構單位的莫耳數，聚乙❹旨中此等單 讨生之結構單位的比例較伟真$曾瓦。/ ” τ j权佳為5莫耳以下，更佳為3蓑 上述PVA只要處於去々 、未知及本發明之效果的範圍 則可經1種或2種以上可推 > 处u ， 進仃接枝共聚合的單體改性。 201224020 為該可進行接枝共聚合的單體可例舉如不飽和磺酸或其 何生物；碳數2〜3〇2α_烯烴等。基於構成PVA之整體結 構早位的莫耳數，PVA中可進行接枝共聚合的單體所衍 生之結構單位的比例較佳為5莫耳％以下。 上述PV A其一部分羥基可經交聯，亦可未交聯。又 ，上述PVA其一部分羥基可與乙醛、丁醛等醛化合物等 反應而形成縮醛結構，亦可未與此等化合物而未形成縮 醛結構。 上述PVA的聚合度較佳處於15〇〇〜6〇〇〇之範圍内更 佳處於1800〜5000之範圍内，再更佳處於2〇〇〇〜4〇〇〇之範 圍内。聚合度低於1500時，會有所得之薄膜的貫穿抵抗 降低的傾向，另一方面，聚合度大於6000時則有導致 w成本提间、製膜時之步驟通過性不良等的傾向。此 外’本說明書中所謂PVA的聚合度係指依據日本工業規 格K6726-1994之記載所測定的平均聚合度。 由所得之薄膜的耐水性方面而言，上述pVA的皂化 度較佳為動莫耳^，更料98 5莫耳％以上，再更 佳為99.0莫耳％以上。皂化度低於％ 〇莫耳％時會有Μ 溶出而使強度降低的傾向。此外，本說明書中之pvA的 =度係指’相對PVA所具有之可經由息化轉換成乙稀 =位的結構單位(典型上為乙稀酿翠位)與乙稀醇單位 ^莫耳數，該乙烯醇單位的莫耳數所占的比例(莫耳W 。息化度可依據曰本工業規格助6_1 994之記載來測定 可使用任何分子内 作為本發明中所使用之聚羧酸 201224020 八有個χ上緩基之化合物。作為此種化合物之實例可例 舉具有羧基之聚合物（含有羧基之聚合物）；丙二酸、琥 $酉文戊一馱、己一酸、馬來酸、富馬酸、衣康酸、鄰 苯二甲酸等分子量500以下的低分子化合物等，可單獨使 用此等當中的1種，亦可併用2種以上。 作為上述含有羧基之聚合物的具體實例可例舉將丙 烯酸、甲基丙烯酸、巴豆酸、馬來酸、富馬酸、衣康酸 、2-(甲基）丙烯醯氧乙基馬來酸、2_(曱基）丙烯醯氧乙基 鄰苯二甲酸、2-(甲基）丙烯醯氧乙基六氫鄰苯二甲酸等具 有羧基之不飽和化合物的丨種或2種以上聚合而得者。又 ，含有羧基之聚合物亦可為將上述具有羧基之不飽和化 合物的1種或2種以上與不具有羧基之不飽和化合物共聚 合而得者。相對構成含有羧基之聚合物的整體結構單位 的莫耳數，上述具有羧基之不飽和化合物所衍生的結構 單位的莫耳數所占的比例較佳處於5〇〜1〇〇莫耳％之範圍 内，更佳處於80〜100莫耳％之範圍内，再更佳處於95〜1〇〇 莫耳％之範圍内，特佳為i 00莫耳％。本發明中作為含 有羧基之聚合物可僅使用丨種含有羧基之聚合物，亦可併 用2種以上的含有羧基之聚合物。 3有缓基之聚合物的數量平均分子量較佳處於 50000〜loooooo之範圍内，更佳處於10〇〇〇〇〜5〇〇〇〇〇之範 圍内。數量平均分子量若低於50000時，會有所得之薄膜 的強度降低的傾向，而超過1000000時，則有調製水溶液 之際其黏度增高而難以進行薄膜的.製造的傾向。 聚羧酸所具有的羧基其一部分或全部可被令和。當 -10- 201224020 聚缓酸所具有的綾基被中和時，被中和之羧基係以形成 納、碎、鎮等金屬之鹽的形態為佳。 作為聚m酸而使用羧基被中和者時，所使用之總聚 羧酸之中和度（相對可被中和之羧基的總莫耳數，被中和 之羧基的莫耳數所占的比例）較佳為20莫耳◦/❶以下，更值 為1 5莫耳％以下。 作為本發明中所使用之聚羧酸，由所得之薄膜的薄 膜強度等觀點而言較佳為含有羧基之聚合物。此外，該 3有羧基之聚合物當令’由獲得性優良且成本亦低而言 ，較佳為聚（曱基）丙烯酸系聚合物及聚（甲基）丙烯醆系聚 cr物之中和物的至少一者，更佳為聚丙烯酸系聚合物及 聚丙烯酸系聚合物之中和物的至少一者，再更佳為聚丙 稀酸系聚合物，特佳為丙烯酸之均聚物。 本發明薄膜係以PVA :聚羧酸=65 : 35〜95 : 5之範圍 内的質量比使用PVA與聚羧酸而形成。Pva與聚羧酸的 質量比若低於上述範圍’所得之薄膜的薄膜強度便會降 低。另一方面，PVA與聚羧酸的質量比若高於上述範圍 則所知之溥膜的養分穿透性會惡化。PVA與聚叛酸的 質量比較佳處於32〜9〇: 10之範圍内，更佳處於7〇 • 30〜85. 15之範圍内。 由提高薄膜強度之觀點而言，本發明薄膜係以未含 有塑化劑為佳，但只要處於未損及本發明之效果的範圍 内，由提高生產性、操作處理性等而言則亦可含有塑化 劑作為塑化劑係較佳使用多元醇，其具體實例可例舉 乙二醇、甘油、丙二醇、二乙二醇、二甘油、三乙二 -11- 201224020 、四乙二醇、=叙田甘工 —2=丙：:：：發明薄膜可含有此等 性得以提升之觀㈣言，較的操作處理 本發明薄膜令之塑化201224020 VI. Description of the Invention: [Technology of the Invention] The present invention relates to a suitable film for a enamel film for plant cultivation, a method for producing the same, and a plant plant using the same. method. More specifically, the use of polyvinyl alcohol and a carboxyl group can be neutralized by the method and the plant using the same; the film formed by the acid, the manufacturer thereof [prior art] in the cultivation of the plant culture A plant cultivation method for inhibiting spoilage of a culture solution by disposing a film *^ Αι ^ Λ ^ 之间 between a culture solution and a plant body has been proposed (see Patent Document 1). For the 亥 亥 亥 膜 membrane, it is important to penetrate the nutrients, and as a film material, it is made of polyvinyl alcohol, cellophane, sputum acetate, cellulose, nitrocellulose, A hydrophilic material such as ethyl cellulose or polyester. When the cultivar is cultivated by the above-mentioned cultivation method, when simply using μμ # Ab, a hydrophilic material still has a penetrating portion which is generated by the roots such as bacteria, and the knife moves to the culture solution to cause the culture. Liquid rot is bad. Zhong Zuo: The method of rooting is to improve the film strength, but only improve the film strength _ k I, strength, nutrient penetration, etc., other than strength). For example, as a method for improving the strength of a polyethylene film, there is a cross-linking guide. However, as disclosed in Patent Documents 2 and 3, polyacrylic acid, a partially neutralized substance thereof, is used as a chelating agent. A film that has been heat treated for a long time has an improved strength, but the nutrient penetration is extremely poor, and it is not suitable for a film for plant cultivation. In addition, in addition to Patent Documents 2 and 3, a thin crucible 201224020 containing a composition obtained by polymerizing methacrylic acid in the presence of a polyethylene glycol is known (refer to Patent Document 4). A film comprising a composition of a specific polyvinyl alcohol and a polymer having a specific carboxyl group (see Patent Document 5), but these films are still to be further improved in terms of film strength. Therefore, a film having high film strength and excellent nutrient penetration is required. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2008-61 503 [Patent Document 2] Japanese Patent Laid-Open No. Hei 6-22022 No. 1 [Patent Document 3] 曰本特开平 7- [Patent Document 4] US Patent No. 2 196 925 0 [Patent Document 5] JP-A-2007-199248 SUMMARY OF INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a film. A suitable film of a film for plant cultivation which has high strength, can suppress the penetration of roots and is excellent in nutrient penetration, and allows the plant body to grow well, a method for producing the same, and a plant cultivation method using the same. [Means for Solving the Problem] The present inventors have made efforts to carry out a plurality of studies for the above-mentioned purposes, and found that a polyethylene resin and a carboxyl group can be neutralized at a mass ratio of 65:3 5 to 95:5. The carboxylic acid forms a film and is subjected to heat treatment under specific conditions to adjust the softening point thereof to 75 to 9 (rc, thereby forming a film strength n, suppressing root penetration and excellent nutrient penetrability and making the plant The present inventors have completed the present invention based on the knowledge gained from the above-mentioned knowledge. 201224020 That is, the present invention relates to [1] a film which is 65 : 35 to 95 · · 5 mass ratio than the use of polyvinyl alcohol (hereinafter referred to as "polyvinyl alcohol" referred to as "PVA") and rebel can be neutralized polycytosis (the following will be "rebel" And polyglycolic acid, which is simply referred to as "polycarboxylic acid", and has a softening point of 75 to 90. (:; [2] The film of [1] wherein the aforementioned polyacid is poly(fluorenyl) At least one of an acrylic polymer and a poly(indenyl) acrylic polymer neutralizing agent; [3 The film [1] or [2] has a penetration resistance of 17.0 Å or more when converted into a thickness of 6 〇 μηη, and the penetration resistance is immersed in water of 2 〇t for 1 minute. Then, the maximum load of the thick round nail (CN65) specified in Japanese Industrial Specification A55〇8: 2〇〇9 is measured; [4] The film according to any one of [1] to [3], a film for cultivating pots and horses; [5] a method for producing a film comprising eight pairs of a film made of a stock solution at a temperature in the range of 130 to 170 ° C. She cooked 6~丨4 minutes, wherein the stock solution was 65:35~95: 5 皙县u·人一分酸; 5 篁 篁 contains PVA and poly [6] 如[5] The manufacturing method, the above-mentioned person, 芨田甘, hard 敁 聚聚(meth)acrylic 4 σ and poly(meth)acrylic polymer, and [7], [5] or [6], Pottery method, /; for the cultivation of the film for plant cultivation, the system is used to make the plant directly connected with the film of [4] [8] a plant cutting method to cut the plant [the effect of the invention] And nutrients are available A suitable film of the 201224020 plant cultivation film which is excellent in the strength of the film and which is excellent in the growth of the roots, and a method for producing the same, and a plant cultivation method using the same. [Embodiment] The present invention will be described in detail below. As the PVA used in the present invention, it can be obtained by saponifying polyethylene vinegar; the polyvinyl ester is vinyl acetate, ethylene formate vinegar, vinyl propionate, Vinyl esters such as vinyl butyrate, trimethyl vinyl acetate, vinyl versatate, vinyl laurate, vinyl hydroxybenzoate, vinyl benzoate, isopropenyl acetate, etc. Species or two or more types of polymerization. Among the above vinyl esters, vinyl acetate is preferred from the viewpoints of easiness of production, availability, cost, and the like of pVA. It is preferable that the above-mentioned polyvinyl ester is produced by using only two kinds of vinyl esters or two or more kinds of vinyl esters as a monomer, and it is more preferable to use only a vinyl ester of the above-mentioned vinyl ester as a monomer, as long as it is not damaged by the present invention. Within the range of effects, it may be a copolymer of a work type or two or more kinds of vinyl esters and other monomers copolymerizable therewith. The other monomer copolymerizable with the above-mentioned vinyl ester may, for example, be a propylene oxide having 2 to 3 carbon atoms such as ethylene, propylene, 1-butene or isobutylene; or methyl ketone (meth)acrylate; Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (methyl) (meth) acrylate such as butyl acrylate, (meth)acrylic acid 2·ethylhexyl ester, (decyl) decyl acrylate, decyl (decyl) acrylate; (fluorenyl) propylene Indoleamine, N-methyl(fluorenyl)propene oxime 201224020 Amine, N-ethyl(fluorenyl) acrylamide, hydrazine, hydrazine-dimethyl(fluorenyl) acrylamide, diacetone (meth) propylene Hydrazine, (fluorenyl) acrylamide propylene sulfonic acid or its salt '(meth) acrylamidopropyl dimethyl hydrazine or its salt, hydrazine-hydroxymethyl (meth) acrylamide or its derivatives, etc. (fluorenyl) acrylamide derivative; Ν-vinylformamide, hydrazine-vinylacetamide, hydrazine-vinylpyrrolidone, etc. Ν-vinyl decylamine; methyl vinyl ether, ethyl Ethylene ether, n-propyl vinyl ether, isopropyl ether ether, n-butyl vinyl fluorene, isobutyl ether ether, tert-butyl butyl ether, lauryl vinyl ether, stearic acid vinyl ether, etc. Ethylene cyanide such as (meth)acrylonitrile; vinyl styrene such as ethylene, ethylene diethylene, vinyl fluoride, and difluoroethylene; allyl compound such as allyl acetate and allyl; vinyl A vinyl mercapto compound such as trimethoxydecane; an unsaturated sulfonic acid or the like. The polyvinyl ester may have one or two or more kinds of structural units derived from the other monomers. The proportion of the structural unit derived from the other monomer in the above polyvinyl ester is preferably 15 mol% or less based on the number of moles constituting the overall structural unit of the polyvinyl ester. More preferably, it is 5 mol% or less. In particular, when the other monomer is a water-soluble monomer such as an unsaturated sulfonic acid which may promote the obtained PVA, the obtained film is used as a film for plant cutting, etc., in order to prevent film dissolution, based on The number of moirs that constitute the overall structural unit of the polyethylene vinegar, the ratio of the structural units of the single-discovery in the purpose of the poly-ethylene vinegar is more than that of Weizheng. / τ 佳 佳 佳 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Modification of the graft copolymerized monomer. 201224020 The monomer capable of graft copolymerization may, for example, be an unsaturated sulfonic acid or a living organism thereof; a carbon number of 2 to 3? 2?-olefin, etc. The molar number of the early structure of the overall structure, the proportion of the structural unit derived from the monomer capable of graft copolymerization in PVA is preferably 5 mol% or less. A part of the hydroxyl groups of the above PV A may be crosslinked or not. Further, a part of the hydroxyl groups of the PVA may react with an aldehyde compound such as acetaldehyde or butyraldehyde to form an acetal structure, or may not form an acetal structure with such a compound. The degree of polymerization of the PVA is preferably at least The range of 15〇〇~6〇〇〇 is better in the range of 1800~5000, and more preferably in the range of 2〇〇〇~4〇〇〇. When the degree of polymerization is less than 1500, there will be a film obtained. The tendency of the penetration resistance to decrease, on the other hand, when the degree of polymerization is greater than 6000, it causes the cost of w In the present invention, the degree of polymerization of PVA in the present invention means the average degree of polymerization measured according to the description of Japanese Industrial Standard K6726-1994. The water resistance of the obtained film. In view of the above, the degree of saponification of the above pVA is preferably motility, more preferably 98 5 mol% or more, still more preferably 99.0 mol% or more. Saponification degree is less than % 〇 mol%% Μ dissolution In addition, the degree of pvA in the present specification means that the relative PVA has a structural unit that can be converted into a vinyl group by localization (typically, the Ethylene Bundle) and B. The molar alcohol unit ^ mole number, the proportion of the molar number of the vinyl alcohol unit (Mohr W. The degree of refinement can be determined according to the description of the industrial specification of 61-3994, which can be used in any of the molecules as the present invention. The polycarboxylic acid used in 201224020 has a compound which has a thiol group. As an example of such a compound, a polymer having a carboxyl group (a polymer having a carboxyl group); malonic acid, succinyl quinone , hexanoic acid, maleic acid, fumaric acid, itacon One of these may be used alone or in combination of a low molecular weight compound having a molecular weight of 500 or less, such as an acid or a phthalic acid, and the like. Acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(indenyl) propylene oxyethyl phthalic acid, 2- A polymer having a carboxyl group-containing unsaturated compound such as (meth)acryloyloxyethylhexahydrophthalic acid or a polymer obtained by polymerizing two or more kinds thereof. Further, the polymer having a carboxyl group may be a carboxyl group. One or two or more kinds of saturated compounds are copolymerized with an unsaturated compound having no carboxyl group. The ratio of the number of moles of the structural unit derived from the unsaturated compound having a carboxyl group is preferably in the range of 5 〇 to 1 〇〇 mol% with respect to the number of moles of the overall structural unit constituting the polymer having a carboxyl group. Preferably, it is in the range of 80 to 100% by mole, and more preferably in the range of 95 to 1% of the mole, and particularly preferably i 00% by mole. In the present invention, as the polymer having a carboxyl group, only a polymer having a carboxyl group may be used, or two or more kinds of polymers containing a carboxyl group may be used in combination. The number average molecular weight of the polymer having 3 retardation is preferably in the range of 50,000 to loooooo, more preferably in the range of 10 Torr to 5 Torr. When the number average molecular weight is less than 50,000, the strength of the obtained film tends to decrease, and when it exceeds 1,000,000, the viscosity tends to increase when the aqueous solution is prepared, and it is difficult to produce a film. Some or all of the carboxyl groups of the polycarboxylic acid may be neutralized. When the sulfhydryl group possessed by -10-201224020 polyacid is neutralized, it is preferred that the carboxy group neutralized to form a salt of a metal such as sodium, granule or town. When a carboxyl group is neutralized as a polym acid, the total polycarboxylic acid used is neutralized (the total number of moles of the carboxyl group which can be neutralized, and the number of moles of the carboxyl group which is neutralized) The ratio is preferably 20 moles/❶ or less, and more preferably 15 mole% or less. The polycarboxylic acid used in the present invention is preferably a carboxyl group-containing polymer from the viewpoint of film strength of the obtained film and the like. Further, the polymer having 3 carboxyl groups is preferably a poly(indenyl)acrylic polymer and a poly(meth)acrylonitrile poly(r) neutralized substance when it is excellent in availability and low in cost. At least one of the polyacrylic polymer and the polyacrylic polymer neutralizer is more preferably a polyacrylic acid polymer, and particularly preferably a homopolymer of acrylic acid. The film of the present invention is formed by using PVA and a polycarboxylic acid in a mass ratio in the range of PVA:polycarboxylic acid = 65:35 to 95:5. When the mass ratio of Pva to polycarboxylic acid is lower than the above range, the film strength of the film obtained is lowered. On the other hand, if the mass ratio of PVA to polycarboxylic acid is higher than the above range, the nutrient permeability of the ruthenium film is deteriorated. The quality of PVA and polyphenolic acid is preferably in the range of 32 to 9 〇: 10, more preferably in the range of 7 〇 • 30 to 85. From the viewpoint of improving the strength of the film, the film of the present invention is preferably not contained in the plasticizer, but may be improved in productivity, handling properties, etc., as long as it does not impair the effects of the present invention. A polyhydric alcohol is preferably used as the plasticizer, and specific examples thereof include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene di-11-201224020, tetraethylene glycol, = 叙田甘工—2=丙:::: The invention film can contain such a view that it can be improved (4), compared with the operation of the film of the invention to plasticize
盥聚翔g# it 1 ηΛ ® 3量相對於所使用之PVA '、眾羧酸共100質量份，較 更佳處於0丨9哲θ 权佳處於0〜20質量份之範圍内， 更佳處於0〜12質量份之範圍 範圍内。 丹更彳圭處於0〜8質量份之 將後述原液用於原料爽迤& 士 2欠ηο ^ 高製膜性、抑制所得之本發明薄膜時，由可提 』所付之薄膜的厚度不均的發生，且於製 膜時使用金屬輥（met丨 m 、裝 〇11)或帶製造薄膜之際，可容易 由此等金屬輥或帶剝離薄膜而言，係以於該 界面活性劑為佳。由摻 生、；以之“ 1。^ 修屁有界面活性劑的原液來製造本 =薄膜時，該薄膜中便含有界面活性劑。上述界面： 而種類並未特別限定，由金屬輥或帶之剝離性觀點 5 ’較佳為㊣離子性界面活性劑或非離子性界面活性 劑’更佳為非離子性界面活性劑。 作為陰離子性界面活性劑’合適者為例如月桂酸鉀 匕羧酸型，聚氧乙烯月桂醚硫酸鹽、辛基硫酸鹽等硫酸 酉θ型’十二烷基苯磺酸鹽等磺酸型等。 、作為非離子性界面活性劑，合適者為例如聚氧乙烯 油酸趟等院基驗型；聚氧乙烯辛基苯基趟等烧基苯基型 ’聚氧乙稀月桂酸酿等烧基醋型；聚氧乙婦月桂基胺基 醚等烷基胺型；聚氧乙烯月桂酸醯胺等烷基醯胺型；聚 氧乙烯聚氧丙烯醚等聚丙二醇醚型；油酸二乙醇醯胺等 烷醇醯胺型；聚烯烴烯丙基苯基醚等烯丙基苯基醚型等 -12- 201224020 此等界面活性劑可1種單獨或2種以上組合使用。 摻混界面活性劑時’相對所使用之PV A與聚缓酸共 100質量份’其摻混量較佳處於〇.〇丨〜0.5質量份之範圍内 ’更佳處於0.02〜0.3質量份之範圍内，再更佳處於 0 · 0 5〜0.1質量份之範圍内》若使界面活性劑的摻混量相對 所使用之PVA與聚羧酸共100質量份為〇·〇1質量份以上 ’可提升製膜性及剝離性。另一方面，若使界面活性劑 的含量相對所使用之PVA與聚叛酸共1〇〇質量份為〇5質 量份以下，則可抑制界面活性劑由所得之薄膜的表面滲 出而發生阻塞（blocking)之情況。 本發明薄膜可視需求進一步含有抗氧化劑、抗凍劑 、pH調整劑、遮蔽劑、著色防止劑、油劑等成分。 本發明薄膜中，PVA及/或聚羧酸所衍生之成分、塑 化劑以及界面活性劑總共所占的比例較佳處於50〜100質 量％之範圍内，更佳處於80〜100質量％之範圍内，再更佳 處於95〜100質量％之範圍内。 本發明薄膜之軟化點需處於75〜90°C之範圍内，較佳 處於76〜88°C之範圍内，更佳處於77〜85°C之範圍内。薄 膜之軟化點若低於75r，薄膜強度便會降低。另一方面 ，薄膜之軟化點若高於9 0 °C則養分穿透性會惡化。此外 ，薄膜之軟化點可於實施例中以後述方法來測定》 本發明包含薄膜之製造方法，其包含對由原液製成 之薄膜以130〜170ec之範圍内的溫度實施熱處理6〜14分 鐘之步驟（熱處理步驟），其中該原液係以65: 35〜95: 5 -13- 201224020 的質量比含有上述PVA與上述聚羧酸。透過該製造方法 ，即可有效且順利地製造上述的本發明薄膜》 作為上述原液可使用溶劑中溶有上述PVA、聚羧酸 及視需求進一步溶有塑化劑、界面活性劑等成分者、含 有PVA、聚羧酸及視需求進一步含有塑化劑、界面活性 劑等成分並使P V A溶融者。此等原液中，各成分係以均 勻混合為佳。 原液中之PVA與聚羧酸的質量比係處於PVA :聚羧 酸= 65: 35~95: 5之範圍内’較佳處於68: 32〜90: 1〇之 範圍内，更佳處於70 : 30〜85 : 15之範圍内。 作為調製原液時所使用的上述溶劑，可例舉如水、 二甲基亞颯、二曱基曱醯胺、二甲基乙醯胺、N_曱基吡 咯啶酮、乙二醇、甘油、丙二醇、二乙二醇、三乙二醇 、四乙一醇、二經甲基丙炫、乙二胺、二乙三胺等，能 使用此等當中的1種或2種以上。其中，由環境負擔、回 收性方面而言較佳為水。 又’原液的揮發分率（製膜時由揮發、蒸發所去除之 溶劑等揮發性成分於原液中的含有比例）係因製膜方法 、製膜條件等而異，惟較佳處於50〜95質量％之範圍内， 更佳處於5 5〜9 0質量％之範圍内。若使原液的揮發分率為 5〇質量％以上’原液的黏度便不會過高，可順利進行原 :調製時的過濾、脫泡’而易於進行雜質、缺陷較少的 ，膜的製造。另-方® ’若使原液的揮發分率為95質量 乂下則原液的濃度不會過低，而易於進行薄膜的工 -14- 201224020 作為原液之調製方法可採用將PVA與聚羧酸混合後 溶於溶劑之方法；將PVA與聚叛酸分別溶於溶劑而^成 溶液後，以適當比例混合兩溶液之方法；於溶劑中使p V a 及聚羧酸的其中一者溶解後使剩餘之聚合物溶解之方法 (例如於PVA溶液中使聚羧酸溶解之方法 一 寸）寻一般混合 方法。惟，將PVA與聚羧酸混合後設為高溫時會有黏度 上升而•以進行製膜的㈣，因&較佳為預丄調製^ PVA溶液’並將其與聚羧酸或其溶液於較低溫下，較佳 為70°C以下混合之方法。 作為由上述原液製造供予熱處理步驟之薄膜時的製 膜方法，可例舉如濕式製膜法、凝膠製膜法、乾式之危 延製膜法、擠壓製膜法等。此等製膜方法可“， 也可組合、採用2種以上。 上述製膜方法當中，較佳為蚀 罕乂佳為使用τ字縫模、斗板 字模、唇式塗布模具dipper.)等 製膜法。作為流延製膜法的具體方法，可例舉如 上而^液排出或流延至旋轉、加熱的轉（或帶）的周面 法。特別是在連續進行流延製膜時，於工 3=用例如此方法：將上述原液均等地排出或 奴轉加熱的輥（或帶）的周面上 ，並使揮發性成分由排出或流 1面上 的肢沾甘+ 飞抓延至5亥輕（或帶）的周面上 的膜的其中一面蒸發而乾 根或多根旋韓、…： 置於其下流側之1 使盆通^献 〇…、的周面上進—步進行乾燥、或 使其通過熱風乾燥裝置 飞 奘署不、，U 步進行乾燥後，以捲繞 置予以捲繞。可適當組合加埶 …视所進仃之乾燥與熱風 -15- 201224020 乾燥裝置所進行之乾燥來實施之。 為將薄膜凋整成適當狀態’則以附設有調濕裝置； 供驅動各親之馬達；變速機等速度調整機構等為佳。 在如上述連續進行流延製膜時，本發明之製造方法 中的熱處理步驟可於針對經捲繞裝置捲繞後的薄膜，視 需求予以捲出後進行，或可於加熱輥、熱風乾燥裝置所 進行之乾燥的中途或乾燥後’即經捲繞裝置捲繞前進行 其中Φ溥膜生產性優良言之，係、以經捲繞裝置捲繞 前進行熱處理步驟為佳。 由可提高熱處31步驟之效果而言，供予熱處理步驟 之薄膜的含水率較佳處於卜15質量％之範圍内，更佳處 於2〜1 3質量％之範圍内。此外，薄膜的含水率可由薄膜 乾燥前後的質量來算出，具體上可由對象薄膜的質量（a) 、與該PVA薄膜於5(rc下經真空乾燥4小.時後的質量（b) ’依下述式（1)來算出》 含水率（質量 ％) = 1〇〇 X [(A-B)/A] (1) 作為熱處理步驟中的熱處理方法可例舉如使其與加 熱輥接觸之方法、吹送熱風之方法等’而由可均勻進行 熱處理而言，較佳為使其與加熱輥接觸之方法。此等熱 處理方法可僅採用1種，也可組合、採用2種以上。 透過熱處理步驟，便可使薄膜中的交聯反應適當地進行 ’由此即可製得軟化點經調整的薄膜。 為使薄膜中的交聯反應適當進行，則熱處理步驟的 溫度係處於130〜17(TC之範圍内，較佳處於n5〜165t：i 範圍内，更佳處於MO-i 6(TC之範圍内。該溫度低於丨3〇t： -16 - 201224020 時’薄膜強度會降低。另一方面，該溫度超過170°C時’ 則養分穿透性會惡化。 為使薄膜中的交聯反應適當地進行，則熱處理步驟 中的熱處理時間係處於6〜14分鐘之範圍内，較佳處於 7〜13分鐘之範圍内，更佳處於8〜12分鐘之範圍内。熱處 理時間若短於6分鐘，便容易造成熱處理不均而難以均勻 地進行交聯反應。另一方面，熱處理時間若長於14分鐘 ’則養分穿透性會惡化。 本發明薄膜係具有高強度。於此，薄膜強度可如後 述實施例中所具體說明，由貫穿抵抗力來評定；該貫穿 抵抗力係以將對象薄膜浸潰於2(rc的水中1分鐘後，穿刺 曰本工業規格A5508 : 2009所規定的粗圓鐵釘（CN65)之 際的最大荷重來測定。即，該貫穿抵抗力愈高，則可判 斷為薄膜強度愈高。貫穿抵抗力在薄膜之軟化點愈高、 厚度愈厚時有愈高之趨勢。作為本發明薄膜其厚度為 60μιη時的貫穿抵抗力（6〇μπ^|_)，較佳為17 〇n以上更 佳為17.5N以上，再更佳為18.0N以上。若使貫穿抵抗力 (60μπι値）處於上述範圍，即可在使用該薄膜作為植物栽 培用薄膜之際更有效地抑制根貫穿該薄膜之情況。.此外 右本發明薄膜的厚度為6 〇 μ m以外時，可利用以該薄膜 的厚度（Χμπι)測定所得之貫穿抵抗力（Χμπι値），依下述式 (2)換算成厚度為60μιη時的値而設為上述貫穿抵抗力 (60μιη値）。 貫穿抵抗力（60μπι値）=貫穿抵抗力（Χμπι値）乂 60/Χ (2) 由貫穿抵抗力 '生產性及操作處理性觀點而言，本 -17- 201224020 發明薄膜的厚度較佳處於10〜200μιη之範圍内’更佳處於 2〇〜〗5〇^^之範圍内，再更佳處於3〇〜ΐ2〇μπι之範圍内特 佳處於40〜100μηΐ2範圍内，此外，薄膜的厚度可測定任 意5處的厚度，以其等之平均値來求得。 本發明薄膜的形狀並未特別限制，可例舉四角形 例如長方形、正方形等）、圓形、三角形等形狀，可視本 發明薄膜的用途、使用形態等來適當設定，惟由可連續 進行製造且易於保管、輸送而言，較佳為長尺寸薄膜經 捲繞成卷狀所形成之形狀。上述長尺寸薄膜的寬度並未 特別限疋’可依據其用途、使用形態等來適當決定，例 如使用本發明薄琪作為植物栽培用薄膜時，若寬度過寬 則有不易照料植物的傾肖，故較佳為2m以下，更佳，於 10-Π〜I5m之範圍内。#使用於植物栽培㈣膜以二的 用途時’長尺寸薄膜的寬度較佳處於1〇cm〜4m之範圍内 去：佳處於5〇cm〜3m之範圍内。又長尺寸薄膜的長度亦 未特別限制，可例示如5〜5〇〇〇m。 本發明薄膜之用途並無特殊限制，惟由薄膜強 二制根的貫穿且養分穿透性亦優良而使植物體得： :子地生長而言’本發明薄膜較佳作為植物栽培用薄膜 使用。若使用本發明薄膜作為植物栽培用薄膜時，可直 =用本發明薄膜’亦可適當進行裁切、重合等而製成 所要之形狀後使用。 作為本發明薄膜充當植物栽培㈣膜的使用方法， =例舉在本發明S膜上栽培植物等、以使植物與本發 月薄膜直接接觸的方式來栽培植物的方法。作為本發明 18 - 201224020 薄膜充當植物栽培用薄膜的具體使用方法可例舉如在 視需求設有凹坑的大地土壤上配置具有所要之形狀的本 發明薄膜，並於其上配置植物體，藉此將大地土壤與植 物體以該薄膜隔離，以勿使其等直接接觸而培育植物體 之方法；在含有植物體之養分的水溶液（培養液）上配置 具有所要之形狀的本發明薄膜，並於其上配置植物體， 藉此將上述水溶液與植物體以該薄膜隔離，以勿使其等 直接接觸而培育植物體之方法。如此一來，便可抑制大 地土壌中的微生物、細菌類、病毒類、殘留農藥等汗染 植物體之情況、或可抑制細菌等經由植物體的根侵入含 有植物體之養分的水溶液中使水溶液腐壞之情況。 [實施例] 對本發明依以下實施例具體進行說明，惟本發明並 未受此等實施例任何限定。 此外，以下實施例及比較例中所採用之薄膜之軟化 點、貫穿抵抗力及養分穿透性’以及根之貫穿試驗的各 測定方法或評定方法係如以下所示。 [薄膜之軟化點的測定方法] 以下實施例或比較例中所得之薄膜之軟化點係使用 第一理化股份有限公司製自動軟化點測定儀r EX-820」 來測定。即，將薄膜切成3 cm見方的大小，將其夾於中央 處開有直徑lcm的圓形孔之厚lmm、虹爪見方的不鏽鋼板 與中央處開有lcm X 2cm的長方形孔之厚1 mm、3 cm見方的 不鏽鋼板間’使開有圓形孔的不镩鋼板侧為上面而設置 於架台上，並將日本工業規格B 15〇1 : 2〇〇9所規定之鋼 -19- 201224020 等級：G60，質量：盥聚翔g# it 1 ηΛ ® 3 is in the range of 0 to 20 parts by mass, more preferably in the range of 0 to 20 parts by mass, relative to the PVA used and 100 parts by mass of the carboxylic acid. Within the range of 0 to 12 parts by mass.丹更彳圭 is in a range of 0 to 8 parts by mass. The raw material to be described later is used for the raw material to be used in the raw material, and the film is not ηο ^ high film forming property, and the obtained film of the present invention is suppressed. When the film is formed by using a metal roll (met丨m, mounting 11) or a film for film formation, it is easy to use such a metal roll or a release film, and the surfactant is good. The film is contained in the film by blending, and the film is prepared by using the original solution of the surfactant. The above interface: the type is not particularly limited, and the metal roll or belt The peeling viewpoint 5 'preferably a positive ionic surfactant or a nonionic surfactant' is more preferably a nonionic surfactant. As an anionic surfactant, a suitable one is, for example, potassium laurate ruthenium carboxylic acid. a sulfonic acid type such as a polyoxyethylene lauryl ether sulfate or an octyl sulfate such as a cerium sulfate θ type 'dodecylbenzenesulfonate or the like. As a nonionic surfactant, a suitable one is, for example, polyoxyethylene.油 油 趟 趟 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Type; polyoxyethylene laurate decylamine and other alkyl guanamine type; polyoxyethylene polyoxypropylene ether and other polypropylene glycol ether type; oleic acid diethanol decylamine and other alkanol oxime type; polyolefin allyl phenyl ether Allyl phenyl ether type, etc. -12- 201224020 These surfactants can be one kind It is used singly or in combination of two or more. When the surfactant is blended, '100 parts by mass of PV A and poly-salted acid used' is preferably in the range of 〇.〇丨~0.5 parts by mass. Preferably, it is in the range of 0.02 to 0.3 parts by mass, more preferably in the range of 0.5 to 0.1 parts by mass." If the amount of the surfactant is blended, 100 parts by mass of the PVA and the polycarboxylic acid used are 〇·〇1 parts by mass or more can improve film forming properties and peeling properties. On the other hand, when the content of the surfactant is 〇5 parts by mass or less based on the total amount of PVA and polyphenolic acid used, Further, it is possible to suppress the occurrence of blocking of the surfactant by oozing out the surface of the obtained film. The film of the present invention may further contain an antioxidant, a cryoprotectant, a pH adjuster, a masking agent, a coloring preventive agent, an oil agent, etc., depending on the demand. In the film of the present invention, the proportion of the component derived from the PVA and/or the polycarboxylic acid, the plasticizer and the surfactant is preferably in the range of 50 to 100% by mass, more preferably 80 to 100% by mass. Within the range of %, even better The softening point of the film of the present invention is in the range of 75 to 90 ° C, preferably in the range of 76 to 88 ° C, more preferably in the range of 77 to 85 ° C. If the softening point of the film is lower than 75r, the film strength will be lowered. On the other hand, if the softening point of the film is higher than 90 ° C, the nutrient penetration will be deteriorated. In addition, the softening point of the film can be used in the embodiment. The method of the present invention includes a method for producing a film comprising a step of heat-treating a film made of a stock solution at a temperature in the range of 130 to 170 ec for 6 to 14 minutes (heat treatment step), wherein the stock solution is 65 : 35~95: 5 -13- 201224020 The mass ratio contains the above PVA with the above polycarboxylic acid. According to the production method, the above-described film of the present invention can be produced efficiently and smoothly. As the raw material liquid, the PVA, the polycarboxylic acid, and the plasticizer, the surfactant, and the like are further dissolved in the solvent. It contains PVA, a polycarboxylic acid, and further contains a plasticizer, a surfactant, and the like as needed, and the PVA is melted. In these stock solutions, it is preferred that the components are uniformly mixed. The mass ratio of PVA to polycarboxylic acid in the stock solution is in the range of PVA: polycarboxylic acid = 65: 35 to 95: 5, preferably in the range of 68: 32 to 90: 1 Torr, more preferably 70: 30 to 85: 15 within the range. The solvent to be used in the preparation of the stock solution may, for example, be water, dimethyl hydrazine, dimethyl decylamine, dimethyl acetamide, N-decyl pyrrolidone, ethylene glycol, glycerin or propylene glycol. And diethylene glycol, triethylene glycol, tetraethylene glycol, dimethicone, ethylenediamine, diethylenetriamine, etc., one or more of these may be used. Among them, water is preferred in terms of environmental burden and recycling. Further, the volatilization rate of the stock solution (the ratio of the volatile component such as the solvent removed by volatilization or evaporation during the film formation to the stock solution) varies depending on the film forming method, the film forming conditions, and the like, but is preferably 50 to 95. Within the range of % by mass, more preferably in the range of 5 5 to 90% by mass. When the volatilization rate of the stock solution is 5% by mass or more, the viscosity of the stock solution is not excessively high, and the filtration and defoaming at the time of preparation can be smoothly performed, and the film can be easily produced with less impurities and defects. --方® 'If the volatilization rate of the stock solution is 95 mass 乂, the concentration of the stock solution will not be too low, and the film can be easily processed. - 201224020 As a stock solution, the PVA can be mixed with the polycarboxylic acid. After dissolving in a solvent; after dissolving PVA and polydox acid in a solvent and forming a solution, mixing the two solutions in an appropriate ratio; dissolving one of p V a and the polycarboxylic acid in a solvent to dissolve The method of dissolving the remaining polymer (for example, one inch of the method of dissolving the polycarboxylic acid in a PVA solution) is to find a general mixing method. However, when the PVA is mixed with the polycarboxylic acid, the viscosity is increased when the temperature is high, and the film is formed (4), and it is preferred to prepare the PVA solution and prepare it with a polycarboxylic acid or a solution thereof. At a lower temperature, a method of mixing below 70 ° C is preferred. The film forming method for producing a film for the heat treatment step from the above-mentioned stock solution may, for example, be a wet film forming method, a gel film forming method, a dry type dangerous film forming method, or an extrusion film forming method. These film forming methods may be used in combination or in combination of two or more. Among the above film forming methods, it is preferable to use a τ word slit die, a bucket plate die, and a lip coat die dipper. As a specific method of the casting film forming method, a circumferential surface method in which the liquid is discharged or cast to a rotating or heated rotating (or belt) as described above can be exemplified, in particular, when casting is continuously performed, Work 3 = using this method: the above-mentioned stock solution is evenly discharged or slaved to the circumferential surface of the heated roll (or belt), and the volatile components are removed from the limbs on the surface of the discharge or the flow to the surface. One side of the film on the peripheral surface of the light (or belt) is evaporated to dry root or a plurality of spins, ...: placed on the downstream side of the film, and the surface of the basin is dried. Or, it can be passed through a hot air drying device, and after drying in U steps, it is wound up by winding. It can be combined and twisted properly... depending on the drying and hot air of the -15-201224020 drying device Drying is carried out. In order to get the film into a proper state, it is provided with humidity control. Preferably, the motor for driving each of the pros; the speed adjusting mechanism such as a shifting machine, etc. The heat treatment step in the manufacturing method of the present invention may be applied to the winding device after being continuously wound and formed as described above. The film may be rolled out as required, or may be carried out in the middle of drying or drying after heating roller or hot air drying device, that is, before the winding device is wound, the Φ film production property is excellent, Preferably, the heat treatment step is performed before winding by the winding device. The water content of the film for the heat treatment step is preferably in the range of 15% by mass, more preferably 2, in terms of the effect of the step of increasing the heat portion 31. In addition, the moisture content of the film can be calculated from the mass before and after the film is dried, specifically, the mass of the target film (a), and the PVA film at 5 (vacuum drying under vacuum 4 hours). The mass after the time (b) 'calculated according to the following formula (1). Water content (% by mass) = 1 〇〇 X [(AB) / A] (1) As the heat treatment method in the heat treatment step, for example, a method of bringing it into contact with a heating roller, In order to heat-process uniformly, it is preferable to make it to contact with a heating roll. These heat-processing methods can be used only one type, and can also combine, and can use it, and it is [ The crosslinking reaction in the film can be appropriately performed. Thus, the softening point-adjusted film can be obtained. In order to properly carry out the crosslinking reaction in the film, the temperature of the heat treatment step is 130 to 17 (TC Within the range, preferably in the range of n5~165t:i, more preferably in the range of MO-i 6 (TC. When the temperature is lower than 丨3〇t: -16 - 201224020, the film strength will decrease. When the temperature exceeds 170 ° C, the nutrient permeability deteriorates. In order to properly carry out the crosslinking reaction in the film, the heat treatment time in the heat treatment step is in the range of 6 to 14 minutes, preferably 7 Within the range of ~13 minutes, it is better within the range of 8 to 12 minutes. If the heat treatment time is shorter than 6 minutes, it tends to cause uneven heat treatment and it is difficult to carry out the crosslinking reaction uniformly. On the other hand, if the heat treatment time is longer than 14 minutes, the nutrient penetration will deteriorate. The film of the present invention has high strength. Here, the film strength can be evaluated by the penetration resistance as specifically described in the examples to be described later; the penetration resistance is obtained by immersing the target film in 2 (rc water for 1 minute, puncture the industrial specification A5508: The maximum load at the time of the round nail (CN65) specified in 2009 is measured. That is, the higher the penetration resistance, the higher the film strength can be judged. The higher the penetration resistance at the softening point of the film, the higher the thickness When the thickness is 60 μm, the penetration resistance (6 〇μπ^|_) is preferably 17 〇n or more, more preferably 17.5 N or more, and still more preferably 18.0 N. When the penetration resistance (60 μm) is in the above range, it is possible to more effectively suppress the penetration of the root through the film when the film is used as a film for plant cultivation. Further, the film of the right invention has a thickness of 6 〇. When it is other than μ m, the penetration resistance (60μπι値) measured by the thickness of the film (Χμπι) is converted into a thickness of 60 μm by the following formula (2), and the penetration resistance (60 μm) is used.値). Resistance (60μπι値) = penetration resistance (Χμπι値) 乂 60 / Χ (2) From the viewpoint of penetration resistance 'productivity and handling efficiency, the thickness of the film of the invention of -17-201224020 is preferably 10~ Within the range of 200μιη, it is better in the range of 2〇~〗 5〇^^, and more preferably in the range of 3〇~ΐ2〇μπι, especially in the range of 40~100μηΐ2, in addition, the thickness of the film can be determined arbitrarily. The thickness of the five places is determined by the average enthalpy of the film. The shape of the film of the present invention is not particularly limited, and may be, for example, a square shape such as a rectangle, a square, or the like, a circle, a triangle or the like, and the use of the film of the present invention may be considered. It is preferable to set it as a form and the like, and it is preferable that the long-length film is wound into a roll shape, since it can be continuously manufactured, and it is easy to store and convey. The width of the long-length film is not particularly limited, and may be appropriately determined depending on the use, the form of use, and the like. For example, when the film of the present invention is used as a film for plant cultivation, if the width is too wide, it is difficult to care for the plant. Therefore, it is preferably 2 m or less, more preferably in the range of 10 Π to I5 m. #Using plant cultivation (4) When the film is used for two purposes, the width of the long-length film is preferably in the range of 1 〇 cm to 4 m. Preferably, it is in the range of 5 〇 cm to 3 m. The length of the long-length film is also not particularly limited, and may be, for example, 5 to 5 μm. The use of the film of the present invention is not particularly limited, but the plant is obtained by the penetration of the strong root of the film and the nutrient penetration is also excellent: in the case of sub-growth, the film of the present invention is preferably used as a film for plant cultivation. . When the film of the present invention is used as a film for plant cultivation, the film of the present invention can be used in the form of a desired shape by appropriately cutting, superposing, or the like. As a method of using the film of the present invention as a plant cultivation (tetra) film, a method of cultivating a plant by directly cultivating a plant or the like on the S film of the present invention so as to directly contact the plant with the film of the present month is exemplified. As a specific method of using the film of the present invention 18 - 201224020 as a film for plant cultivation, for example, a film of the present invention having a desired shape is disposed on a soil having pits as required, and a plant body is disposed thereon. a method of isolating the soil from the plant body by the film so as not to be in direct contact with the plant body; and arranging the film of the invention having the desired shape on the aqueous solution (culture solution) containing the nutrients of the plant body, and A method in which a plant body is disposed thereon, thereby isolating the aqueous solution from the plant body by the film, thereby cultivating the plant body without directly contacting it. In this way, it is possible to suppress the sweaty plant body such as microorganisms, bacteria, viruses, and residual pesticides in the earthworms, or to inhibit the penetration of bacteria into the aqueous solution containing the nutrients of the plant body through the roots of the plant. Corruption. [Examples] The present invention is specifically described by the following examples, but the present invention is not limited by the examples. Further, the respective measurement methods or evaluation methods of the softening point, penetration resistance, and nutrient penetration' of the film used in the following examples and comparative examples and the root penetration test are as follows. [Method for Measuring Softening Point of Film] The softening point of the film obtained in the following examples or comparative examples was measured using an automatic softening point measuring instrument r EX-820 manufactured by Seiko Ryoichi Co., Ltd. That is, the film is cut into a size of 3 cm square, and it is sandwiched at the center by a circular hole having a diameter of lcm, a thickness of lmm, a stainless steel plate of a rainbow claw square, and a thickness of a rectangular hole having a diameter of 1 cm X 2 cm at the center. Between the stainless steel plates of mm and 3 cm squares, the side of the stainless steel plate with a circular hole is placed on the frame and the steel -19- specified in Japanese Industrial Standard B 15〇1 : 2〇〇9 201224020 Grade: G60, quality:
90」。 球（稱呼· 3/8(直徑9.525mm)，等級：G6 3.5g±0.05g)載置於位於圓形孔中央的薄膜上 [薄膜之貫穿抵抗力的測定方法] 將以下實施例或比較例所得之薄膜切成3cm見方的 大小，並次潰於20 C、1 〇〇〇g的蒸餾水中。浸潰i分鐘後 取出薄膜， 將其夾於令央處開有直徑1 crn的孔之厚1 mm 、3cm見方的2片不鏽鋼板之間，並以夾子保留出左右2 處。次之’將上述樣本固定於島津製作所股份有限公司 製桌上型精密萬能試驗機「Autograph AGS-J」的下側夾 持器（gripper)上，將日本工業規格A55〇8: 2〇〇9所規定的 粗圓鐵釘CN65固定於上側夾持器上，並以速度i〇〇mm/ 分穿刺位於不鏽鋼板之孔的中央的薄膜。以此時的最大 荷重作為貫穿抵抗力（單位：N)。此外，為防止薄膜乾燥 ，係於3 0秒以内實施浸潰於水中、取出後至穿刺為止之 作業。又’測定溫度係設為2(Tc。當貫穿抵抗力（6〇μπι 値）為17.01^以上時評為「〇」（良好），貫穿抵抗力（6(^111 値）低於17.0Ν時則評為「X」（不良）。 [薄膜之養分穿透性的評定方法] 於缽（bowl)内側配置笊（笳籬），並於笊上配置以下實 施例或比較例所得之薄膜。次之’在缽與薄膜之間添加 '/農度5 %的葡萄糖水溶液1 5 〇 g ’並於薄膜上添加蒸餾水 -20- 201224020 1 5 0 g ’由此將葡萄糖水溶液與蒸餾水以薄膜隔離。接著 ’為防止水分蒸發，而將整體以聚二氣亞乙烯薄膜包覆 。將其於2 3 C下放置2 4小時後’對妹側液（最初之葡萄糖 水溶液）及笊側液（最初之蒸餾水）各者測定葡萄糖濃度。 當兩濃度差小於2.0%時評為「〇」（良好），2·〇%以上時 則評為「X」（不良）。此外’上述評定十葡萄糖濃度係指 使用Thermo Fisher SCIENTIFIC股份有限公司製數位折 射計「AR200」所測定的Brix濃度。 [根的貫穿試驗] 將培養液（HYPONeX JAPAN股份有限公司製「 HYPONeX」EC = 2經稀釋200倍者）200g加入缽内，並將以 下實施例或比較例所得之薄膜配置成其單面與培養液接 觸。在PV A薄膜上放置椰子殼碎片5〇g當作土壤，並播下 草坪種子（TAKII股份有限公司製西洋草坪「Bentgrass Highland」）’以喷水器（sprayer)充分供水’且為防止乾 燥而將整體以聚二氣亞乙稀薄膜包覆。將其置於15〜25^ 的室内，並使用人工燈進行栽培。此外，在草坪生長而 與聚二氣亞乙烯薄膜接觸後，即除去聚二氣亞乙烯薄膜 。‘根貝穿》專膜之日為栽培後150曰以上時評為「〇」（ 良好），短於150日時則評為「X」（不良）。 [實施例1] 相對乙酸乙烯酯之均聚物皂化所得之PVA(聚合度 2400，皂化度99.9莫耳％) 1〇〇質量份，添加界面活性劑聚 氧乙烯月桂醚硫酸鈉0 · 1質量份，加入蒸餾水使PVA濃度 達10質量％ ’並於95°C下攪拌3小時來製作PVA水溶液。 -21- 20 201224020 將該PVA水溶液冷卻至6〇。(：，相對PVA 80質量份，以 質量份的比例添加數量平均分子量1 50000的聚丙烯酸 於6〇°C下充分攪拌至呈均勻而製成製膜原液。其後， 6〇°C的金屬輥上流延製膜原液並乾燥至含水率達3質 %’接著以150X：實施熱處理10分鐘來製作厚60μιη的薄 〇 利用所得之薄膜，依循上述方法測定或評定薄膜 軟化點、貫穿抵抗力及養分穿透性，並進一步進行根 貝穿S式驗。結果係示於表1。 [實施例2] 除相對PVA 70質量份以30質量份的比例使用聚内 酸來取代實施例1中相對PVA 80質量份以20質量份的 例使用聚丙烯酸以外，係以與實施例1同樣的方法來製 厚6 0μιη的薄膜。 利用所得之薄膜，依循上述方法測定或評定薄膜 軟化點、貫穿抵抗力及養分穿透性，並進一步進行根 貫穿斌驗。結果係示於表1。 [實施例3] 除相對PVA 90質量份以1 〇質量份的比例使用聚丙 酸來取代實施例1中相對PVA 80質量份以2〇質量份的 例使用聚丙烯酸以外，係以與實施例1同樣的方法來製 厚60μηι的薄膜。 利用所得之薄膜，依循上述方法測定或評定薄膜 軟化點、貫穿抵抗力及養分穿透性，並進一步進行根 貫穿试驗。結果係示於表1。 於 量 m 之 的 烯 比 作 之 的 烯 比 作 之 的 -22- 201224020 [實施例4〜7及比較例1〜6] 除將實施例1中熱處理之溫度·或時間改為表1所示者 以外，係以與實施例1同樣的方法來製作厚60μπι的薄膜 〇 利用所得之薄膜，依循上述方法測定或評定薄膜之 軟化點、貫穿抵抗力及養分穿透性’並進一步進行根的 貫穿试驗。結果係不於表1。 [比較例7] 除相對Ρ V A 6 0質量份以4 0質量份的比例使用聚丙婦 酸來取代實施例1中相對PVA 80質量份以20質量份的比 例使用聚丙烯酸以·外’係以與實施例1同樣的方法來製作 厚60μηι的薄膜。 利用所得之薄膜，依循上述方法測定或評定薄膜之 軟化點、貫穿抵抗力及養分穿透性，並進一步進行根的 貝穿S式驗。結果係示於表1。 [比較例8 ] 除未添加實施例1中的聚丙烯酸而直接使用ρν Α水 溶液作為製膜原液以外係以與實施例丨同樣的方法來製 作厚60μπι的薄膜。 利用所得之薄膜’依循上述方法測定或評定薄膜之 2化點、貫穿抵抗力及養分f透性，並進一步進行根的 貝穿δ式驗。結果係示於表1。 [比較例9及10] 除將比較例8中熱處理之溫度或時間改為表丨所示者 以外，係以與比較例8同樣的方法來製作厚6〇口瓜的薄膜 -23- 201224020 利用所得之薄膜，依循上述方法測定或評定薄膜之 軟化點、貫穿抵抗力及養分穿透性，並進一步進行根的 貫穿試驗。結果係示於表1。 [比較例11 ] 混合含有乙酸乙烯酯之均聚物皂化所得之PVA(聚 合度2400，皂化度99.9莫耳％)2()質量％之水溶液4〇質量 份、甲基丙烯酸4質量份及水丨〇質量份，以9(Γ(：加熱i 6 小時使甲基丙稀酸聚合後，對所得之組成物進行流延製 膜。對進行流延製膜中的乾燥後所得之薄膜以14〇〇C實施 熱處理5分鐘來製作厚60μπι的薄膜。 利用所得之薄膜，依循上述方法測定或評定薄膜之 軟化點、貫穿抵抗力及養分穿透性，並進一步進行根的 貫穿試驗。結果係示於表1。 [比較例12] 將含有乙酸乙烯酯之均聚物皂化所得之PVA(聚合 度2400 ’皂化度99.9莫耳％) 1 〇〇質量份、重量平均分子量 5000的聚丙烯酸（和光純藥工業股份有限公司製）1〇質量 份及甘油12質量份之PVA水溶液（ρνΑ濃度（i 1 〇質量％) 於60C的金屬粮上乾燥而製得厚75μιη的薄膜。將所得之 薄膜固定於框上並以120°C實施熱處理3分鐘。 利用熱處理後之薄膜，依循上述方法測定或評定薄 膜之軟化點、貫穿抵抗力及養分穿透性，並進一步進行 根的貫穿試驗。結果係示於表1。 • 24 - 201224020 [表l] 薄膜 ----一 — 果 — ----1 ff-S* 44- 用量 熱處理條侔 軟化點 貫穿抵抗力 (60μιη 值） ---- 養分 (濃 PVA PAA P1) 溫度 時間 穿透性 度差） 根的 貫穿 試驗 質量份 質量份 °C 分 °c Ν 評定 ---— % ----- 實施例1 80 20 150 10 80.5 18.9 〇 11 ‘评定— /-Ν 實施例2 70 30 150 -!〇 84.4 19.6 〇 1 · «3 】.4Ί 一 Ο〜 〇 實施例3 90 10 150 10 77.1 17.5 〇 1.2 〇 實施例4 80 20 140 _ 10 76.0 17.1 〇 1.2 〇 實施例5 80 20 160 10 89.4 19.3 〇 1.4 1—_ - 〇 實施例6 80 20 150 ‘8 78.2 17.9 〇 ---—. 1.3 〇 ~~ 實施例7 80 20 150 12 81.3 19.1 〇, 1.3 〇 〇 比較例1 80 20 150 5 71.5 11.2 1.0 〇 比較例2 80 20 150 15 >90 23.2 〇 1.6 X 八 〇 比較例3 80 20 120 10 68.0 11.4 X 1.0 〇 V 比較例4 80 20 120 5 68.8 11.7 X 1.0 Ο " -- X 比較例5 80 20 180 10 >90 19.9 〇 3.9 X 〇 比較例6 80 20 180 5 >90 19.0 〇 2.5 X 〇 比較例7 60 40 150 10 >90 4.9 X 1.5 〇 X 比較例8 100 0 150 10 73.2 14.0. X 1.0 〇 X 比較例9 100 0 200 10 79.0 18.4 〇 3.8 X 〇 比較例10 100 0 100 10 64.0 6.9 X 0.5 〇 X 比較例11 (*2) (*2) 140 5 69.5 11-7. X 1.1 〇 X 比較例12 100 10 120 3 64.2 6.1 一 。X 1.0 〇 X n:「paa」係表示聚丙烯酸。 *2 :相對PVA100質量份，係使用曱基丙烯酸50質量份。 實施例1〜7中，貫穿抵抗力、養分穿透性及根的貫穿 試驗的評定結果皆為「〇」（良好），係得薄膜強度高、 玎抑制根的貫穿且養分穿透性亦優良而使植物體得以良 好地生長之植物栽培用薄膜的適用薄滕。另一方面’比 較例1〜1 2中未得貫穿抵抗力、養分穿透性及根的貝穿试 驗皆良好的PVA薄膜。 -25- 201224020 [產業上之可利用性] 本發明薄膜其薄膜強度高、可抑制根的貫穿且養分 穿透性亦優良而使植物體得以良好地生長，從而能夠在 栽培較大的果菜、葉菜而非僅為花草時較佳地用作植物 栽培用薄膜。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 -26-90". Ball (referred to as 3/8 (diameter 9.525 mm), grade: G6 3.5 g ± 0.05 g) placed on a film located at the center of a circular hole [Method for measuring the penetration resistance of a film] The following examples or comparative examples The obtained film was cut into a size of 3 cm square and was crushed in 20 C, 1 〇〇〇g of distilled water. After immersing for 1 minute, the film was taken out and sandwiched between two stainless steel plates of 1 mm thick and 3 cm square with a hole having a diameter of 1 crn at the center, and the left and right sides were retained by clips. The second sample was fixed on the lower gripper (gripper) of the "Autograph AGS-J", a desktop precision universal testing machine manufactured by Shimadzu Corporation. The Japanese industrial specification A55〇8: 2〇〇9 The predetermined thick round nail CN65 is fixed to the upper holder, and the film located at the center of the hole of the stainless steel plate is pierced at a speed of i〇〇mm/min. The maximum load at this time is taken as the penetration resistance (unit: N). Further, in order to prevent the film from drying, the operation of immersing in water and taking out the puncture is performed within 30 seconds. In addition, the measurement temperature is set to 2 (Tc. When the penetration resistance (6〇μπι) is 17.01^ or more, it is rated as "〇" (good), and the penetration resistance (6 (^111 値) is less than 17.0". It is rated as "X" (defective). [Method for evaluating nutrient penetration of film] 笊 (fence) is placed inside the bowl, and the film obtained in the following examples or comparative examples is placed on the crucible. 'Add '5 〇g' of a 5 % aqueous glucose solution between the mash and the film and add distilled water to the film -20- 201224020 1 5 0 g 'This isolates the aqueous glucose solution from the distilled water as a film. In order to prevent evaporation of water, the whole is coated with a polyethylene dioxide film. After being placed at 2 3 C for 24 hours, 'the side liquid (the initial aqueous glucose solution) and the side liquid (the original distilled water) Each person measures the glucose concentration. When the difference between the two concentrations is less than 2.0%, it is rated as "〇" (good), and when the difference is more than 2%, it is rated as "X" (bad). In addition, the above-mentioned evaluation of ten glucose concentration refers to the use of Thermo Fisher. Digital refractometer manufactured by SCIENTIFIC Co., Ltd. Brix concentration measured by AR200" [Peer penetration test] 200 g of a culture solution (HYPONeX JAPAN Co., Ltd. "HYPONeX" EC = 2 diluted 200 times) was added to the crucible, and the following examples or comparative examples were obtained. The film was placed in contact with the culture solution on one side. 5 〇g of coconut shell fragments were placed on the PV A film as soil, and the lawn seeds (Bentgrass Highland) made by TAKII Co., Ltd. were sprayed with water. The sprayer is fully supplied with water and is covered with a polyethylene dioxide film to prevent drying. It is placed in a room of 15 to 25 cm and cultivated using artificial lamps. In addition, it grows on the lawn. After the contact of the polyethylene dioxide film, the polyethylene vinylene film was removed. The date of the 'Genbei wear' film was rated as "〇" (good) for 150曰 or more after cultivation, and was rated as less than 150 days. X" (bad). [Example 1] PVA obtained by saponification of a homopolymer of vinyl acetate (degree of polymerization 2400, degree of saponification 99.9 mol%) 1 part by mass, surfactant added polyoxyethylene lauryl ether Sodium sulfate 0 · 1 mass A PVA aqueous solution was prepared by adding distilled water to a PVA concentration of 10% by mass' and stirring at 95 ° C for 3 hours. -21 - 20 201224020 The PVA aqueous solution was cooled to 6 Torr. (:, relative to PVA 80 parts by mass, by mass The ratio of the parts is added to the polyacrylic acid having a number average molecular weight of 150,000, and the mixture is sufficiently stirred until uniform at 6 ° C to prepare a film forming stock solution. Thereafter, the film forming stock solution is cast on a metal roll of 6 ° C and dried to a moisture content. Up to 3%%' followed by 150X: heat treatment for 10 minutes to make a thin film of 60 μm thick. Using the obtained film, the film softening point, penetration resistance and nutrient penetration were measured or evaluated according to the above method, and further root penetration was performed. S test. The results are shown in Table 1. [Example 2] The same procedure as in Example 1 was carried out except that polylactic acid was used in an amount of 30 parts by mass relative to 70 parts by mass of PVA, instead of 80 parts by mass of the relative PVA in Example 1, and 20 parts by mass of polyacrylic acid was used. The method is to produce a film with a thickness of 60 μm. Using the obtained film, the film softening point, penetration resistance and nutrient penetration were measured or evaluated according to the above method, and the root penetration test was further carried out. The results are shown in Table 1. [Example 3] Except that polyacrylic acid was used in an amount of 1 part by mass relative to 90 parts by mass of PVA, instead of 80 parts by mass of the relative PVA in Example 1, 2 parts by mass of polyacrylic acid was used, and Example 1 was used. The same method was used to make a film having a thickness of 60 μm. Using the obtained film, the film softening point, penetration resistance, and nutrient penetration were measured or evaluated in accordance with the above method, and the root penetration test was further carried out. The results are shown in Table 1. -22-201224020 [Examples 4 to 7 and Comparative Examples 1 to 6] in which the ratio of the olefin to the ratio of the olefins in the amount of m is changed except that the temperature or time of the heat treatment in Example 1 is changed as shown in Table 1. A film having a thickness of 60 μm was produced in the same manner as in Example 1 using the obtained film, and the softening point, penetration resistance, and nutrient penetration of the film were measured or evaluated according to the above method, and the root penetration was further carried out. test. The results are not in Table 1. [Comparative Example 7] Polyacrylic acid was used in an amount of 40 parts by mass relative to Ρ VA 60 parts by mass, and 80 parts by mass of the relative PVA in Example 1 was used in an amount of 20 parts by mass in terms of 20 parts by mass. A film having a thickness of 60 μm was produced in the same manner as in Example 1. Using the obtained film, the softening point, penetration resistance and nutrient penetration of the film were measured or evaluated according to the above method, and the root penetration S test was further carried out. The results are shown in Table 1. [Comparative Example 8] A film having a thickness of 60 μm was produced in the same manner as in Example 除 except that the polyacrylic acid in Example 1 was not used and the ρν Α aqueous solution was directly used as the film forming stock solution. Using the obtained film, the film was measured or evaluated according to the above method, and the penetration resistance and nutrient f permeability of the film were measured, and the root penetration δ test was further carried out. The results are shown in Table 1. [Comparative Examples 9 and 10] A film of a thick 6-mouth melon was produced in the same manner as in Comparative Example 8 except that the temperature or time of the heat treatment in Comparative Example 8 was changed to that shown in Table -23-201224020. The obtained film was subjected to the above method to measure or evaluate the softening point, penetration resistance and nutrient penetration of the film, and further subjected to root penetration test. The results are shown in Table 1. [Comparative Example 11] A PVA obtained by saponification of a homopolymer containing vinyl acetate (degree of polymerization 2400, degree of saponification 99.9 mol%) 2 (% by mass) of an aqueous solution 4 parts by mass, 4 parts by mass of methacrylic acid, and water丨〇 mass parts, 9 (Γ (: heating i 6 hours after the polymerization of methyl methacrylic acid, the resulting composition was cast and formed into a film. The film obtained after drying in the casting film was 14 〇〇C was subjected to heat treatment for 5 minutes to prepare a film having a thickness of 60 μm. Using the obtained film, the softening point, penetration resistance, and nutrient penetration of the film were measured or evaluated according to the above method, and the root penetration test was further carried out. [Table 1] [Comparative Example 12] PVA obtained by saponifying a homopolymer containing vinyl acetate (degree of polymerization: 2400 'saponification degree: 99.9 mol%) 1 〇〇 by mass, polyacrylic acid having a weight average molecular weight of 5,000 (and pure light) Pharmaceutical Co., Ltd.) 1 part by mass and 12 parts by mass of glycerin PVA aqueous solution (ρνΑ concentration (i 1 〇 mass%) was dried on 60 C of metal grain to obtain a film having a thickness of 75 μm. The obtained film was fixed at On the box The heat treatment was carried out for 3 minutes at 120 ° C. Using the heat-treated film, the softening point, penetration resistance and nutrient penetration of the film were measured or evaluated according to the above method, and the root penetration test was further carried out. The results are shown in Table 1. 24 - 201224020 [Table l] Film----一- Fruit--1 ff-S* 44- Heat treatment strip 侔 Softening point penetration resistance (60μιη值) ---- Nutrient (concentrated PVA PAA P1 ) Temperature time penetration difference) Root penetration test mass parts °C minutes °c 评定 Evaluation -----% ----- Example 1 80 20 150 10 80.5 18.9 〇11 'Assessment — /-实施 Example 2 70 30 150 -! 〇 84.4 19.6 〇 1 · «3 】.4 Ί 1 Ο 〇 Example 3 90 10 150 10 77.1 17.5 〇 1.2 〇 Example 4 80 20 140 _ 10 76.0 17.1 〇 1.2 〇 Implementation Example 5 80 20 160 10 89.4 19.3 〇 1.4 1 - _ - 〇 Example 6 80 20 150 '8 78.2 17.9 〇----. 1.3 〇~~ Example 7 80 20 150 12 81.3 19.1 〇, 1.3 〇〇Compare Example 1 80 20 150 5 71.5 11.2 1.0 〇Comparative Example 2 80 20 150 15 >90 23.2 〇1.6 X VIII 〇Comparative Example 3 80 20 120 10 68.0 11.4 X 1.0 〇V Comparative Example 4 80 20 120 5 68.8 11.7 X 1.0 Ο " -- X Comparative Example 5 80 20 180 10 > 90 19.9 〇3.9 X 〇Comparative Example 6 80 20 180 5 > 90 19.0 〇 2.5 X 〇 Comparative Example 7 60 40 150 10 > 90 4.9 X 1.5 〇X Comparative Example 8 100 0 150 10 73.2 14.0. X 1.0 〇X Comparative Example 9 100 0 200 10 79.0 18.4 〇 3.8 X 〇 Comparative Example 10 100 0 100 10 64.0 6.9 X 0.5 〇X Comparative Example 11 (*2) (*2) 140 5 69.5 11-7. X 1.1 〇X Comparative Example 12 100 10 120 3 64.2 6.1 I. X 1.0 〇 X n: "paa" means polyacrylic acid. *2: 50 parts by mass of thioglycolic acid was used in 100 parts by mass of PVA. In Examples 1 to 7, the evaluation results of the penetration resistance, nutrient penetration, and root penetration test were all "〇" (good), and the film strength was high, the root penetration was suppressed, and the nutrient penetration was excellent. The thin film of the plant cultivation film which allows the plant body to grow well. On the other hand, in Comparative Examples 1 to 12, a PVA film which was excellent in penetration resistance, nutrient penetration, and root penetration test was not obtained. -25-201224020 [Industrial Applicability] The film of the present invention has high film strength, can suppress penetration of roots, and is excellent in nutrient penetrability, so that plant bodies can be grown well, and it is possible to cultivate large fruits and vegetables. Leafy vegetables are preferably used as a film for plant cultivation when they are not only flowers and plants. [Simple description of the diagram] None. [Main component symbol description] None. -26-