TW201037023A

TW201037023A - Shield film and shield laminator using same

Info

Publication number: TW201037023A
Application number: TW099101447A
Authority: TW
Inventors: Atsushi Maehara; Norikazu Matsui; Kenji Minato
Original assignee: Unitika Ltd
Priority date: 2009-01-21
Filing date: 2010-01-20
Publication date: 2010-10-16
Also published as: WO2010084846A1; JPWO2010084846A1

Abstract

A shield film having a shield degree equal or higher than 0.3, and containing a shield material and a polyamide resin is provided. The shield material is a white series shield material, and the preferred whiteness degree is 65 to 100%. For example, the film is to contain a titanium oxide 5 to 40 mass% and a polyamide resin 60 to 95 mass%. The shield laminator has at least three layers including a barrier resin layer, a polyamide resin constituted by a shield film and a sealant layer. The shield laminator has a shield degree equal or higher than 0.3, and a oxygen permeability equal or less than 100ml/(m<SP>2</SP>.day.Mpa).

Description

201037023 . . . 六、發明說明：【發明所屬之技術領域】本發明是有關遮蔽性膜及使用該膜之遮蔽性積層體，例如，可作為各種食品包裝材料、尤其作為袋類之内層使用之遮蔽性膜及使用該膜之遮蔽性積層體。【先前技術】作為賦予遮蔽性之熱塑性膜者，已知有：將含有大量無機粒子或有機粒子等顏料的樹脂層積層在熱塑性薄膜之表面者、或將顏料直接添加到熱塑性樹脂中者。作為積層樹脂層之薄膜者，例如，在JP11-34205A中，揭示一種具備有白色的第1印刷層與經施加高遮光性色彩的第2印刷層之包裝材、具備有著色樹脂層之包裝材、或併用兩者之包裝材，分別使全光線穿透率成為30%以下者。然而，設置著色樹脂層，取代設置作為印刷印墨層之複數層的第1印刷層與第2印刷層者，雖可得到遮光性、遮蔽〇性，但為了賦予遮光性而必需要設置1層新的樹脂層，導致會有在製造步驟方面或成本方面的問題。將顏料直接添加到熱塑性樹脂中作成熱塑性薄膜者，例如在JP2001-1 1210A中，揭示一種在聚酯樹脂中添加二氧化鈦或碳酸鈣等無機物的白色薄膜。然而，所得之聚酉旨薄膜雖可以賦予白色性，但不能低比重化，而薄膜變得太堅硬，會有難適用於需要耐衝擊性、耐彎曲疲勞性之各種食品包裝材料等之問題。另一方面，作為包裝材料者，已知有具備有尼龍薄膜 3 321749 201037023 層和密封雜脂薄膜層之至少2層的積層體。尼龍薄膜層主要是用以防止在輸送時之衝擊或因與内容物磨擦而產生的針孔或袋破裂之層。密封劑樹脂薄膜層，係由用以將包裝材料熱密封之聚乙烯或聚丙烯等聚烯烴樹脂形成之層。在包裝食品等之包裝品中，内容物很容易劣化。例如月曰係在點心、巧克力、花生、油炸物等食品中含量报多，仁报谷易因光或氧氣之影響而引起變質或劣化。因此，含有油脂之食品之包I’需要用以充分遮光之遮蔽性、與用以可進行以脫氧氣為目的之氣體置換包裝的氧氣阻隔性。作為遮蔽性與氧氣阻隔性優良之包裝材料者，除了有上述之尼龍薄膜層和密封劑樹脂薄膜層的2層之外，已知有再積層銘荡之薄膜。然而，使用㈣之包裝材料，當使用金屬探測機等進行檢查混入在内容物之金屬片（異物）等之際！呂會與金屬探測機反應，而極固難探測出金屬片（異物）進#’由於利用微波爐加熱時，會自紹箱產生火花產生針孔’故也有不適合微波爐力口熱之問題。因此，脫鋁成為食品包裝業界之課題。於疋，作為氧氣阻隔層而使用透明蒸錢薄膜者，已知有在提高麵性之目狀㈣白色 =:作成透明蒸鍍尼朗膜/白色密封劑層的3層積^。此積層體可具備有某種程度之遮光性與遮蔽性。 ::二=分之情形由於密封劑層是直接與食品接觸，摻 =層之氧化鈦會吸收食品油’結果會有構成袋子内面的岔封劑部分會像柚子皮一樣堆積而發生所謂的「柚 321749 4 201037023 · « . 子皮化」，而損害包裝材品質之問題。於是，作為在直接接觸内容物的密封劑層中不使用鈦之包裝材者，於JP10-305513A中，揭示一種藉由印刷印墨設置連續印刷膜之遮光性積層體。又，如上述，在JP 11-34205A中，揭示一種同時設置印刷層與著色樹脂層之包裝材。【發明内容】 0 (發明欲解決之課題）本發明之課題是提供可以具有各種食品包裝材料等需要之耐衝擊性、耐彎曲疲勞性，且因製造步驟簡略而不增加製造成本，且穿刺強度、遮蔽性、遮光性優異，並且由於無銘（aluminium less)而可在微波爐中加熱之遮蔽性膜。 (解決課題之手段）本發明人等經過專心研究之結果，發現在聚醯胺樹脂中含有一定量之遮蔽材而可以解決前述課題，遂而完成本 €)發明。即，本發明是有關要旨為以下之（1)至（14)者。 (1) 一種遮蔽性膜，其特徵為含有遮蔽材與聚醯胺樹脂，而遮蔽度是在0. 3以下。 (2) 如（1)之遮蔽性膜，其中，遮蔽材為白色系遮蔽材，白色度為65至100%。 (3) 如（2)之遮蔽性膜，其中，含有氧化鈦5至40質量％，並且含有聚醯胺樹脂60至95質量％。 (4) 如（2)之遮蔽性膜，其係在含有氧化鈦10至60質 5 321749 201037023 量°/〇並且含有聚醯胺樹脂40至90質量％之第1層的至少單面上積層由不含氧化鈦之聚醯胺樹脂所構成之第2層而成的積層體，其穿刺強度在7.5 N以上。 (5) 如（2)至（4)中任一項的遮蔽性膜，其中，聚醯胺樹脂之主成分為尼龍6。 (6) 如（2)至（5)中任一項的遮蔽性膜，其係進行同時雙軸延伸而成者。 (7) —種遮蔽性積層體，係至少具有阻隔樹脂層（X)、由上述（1)至（6)中任一項的遮蔽性膜構成之聚醯胺樹脂層 (Y)、與密封劑層（Z)等3種類之層，其遮蔽度為0. 3以上，氧氣穿透度為l〇〇ml/(m2· day · MPa)以下。 (8) 如（7)之遮蔽性積層體，其中，水蒸氣穿透度為 100g/(m2 · day)以下。 (9) 如（7)至（8)之遮蔽性積層體，其中，在20°Cx65%RH 環境下實施重覆5000次之彎曲疲勞測試時的針孔產生個數為20個以下。 (10) 如（7)至（9)中任一項的遮蔽性積層體，其中，白色度為60至100%。 (11) 一種包裝材料，其係由上述（7)至（10)中任一項的遮蔽性積層體所構成。 (發明之效果）本發明之遮蔽性膜，因為含有聚酸胺樹脂，而彎曲性強且可抑制針孔的產生，因此，作為包裝材料使用之際可以使氣體洩漏或混入成為最少限度。根據本發明，由於含 6 321749 201037023 =化==遮蔽性，—含㈣)，層與不含有氣化鈦層之多情形，形成含有氧化欽度等機械特性更加了構，可以使抗張強度/抗張伸根據本發明之遮蔽性 Ο 性與氧氣阻m之積P _，可以提供有充分之遮蔽脂之食。積層體° _層體，尤其在作為含有油物品質：使用時’可以抑制因氧化而造成的内容 ⑼t發月之遮蔽性積層體，因為並非在密封劑層而是在材料胺樹月日層含有氧化鈦而料遮蔽性，所以在構成包裝六;η %内各物不直接與氧化欽接觸。於是，不會因逸封劑層之所謂的柚子皮化而損害包裝材料品質，或鈦混入内容物。 ❹作本發明之遮蔽性積層體，由於使用聚醯胺樹脂層’而 ^曲度強且可以抑制針孔的產生，因此作為包裝材料使用之際，可以使氣體洩漏或混入成為最少限度。本發明之遮蔽性積層體，有氧氣阻隔性也有水蒸氣阻十生，太此可以適用為含有水分之内容物之包裝材料。本發明之遮蔽性積層體，因為即使不使用鋁箔也可以。予，蔽性與氧氣阻隔性，故在作為包裝材料使用之際，藉由金屬探測機檢查異物、或藉由微波爐加熱。【實施方式】實施發明之最佳形態： 7 321749 201037023 以下，詳細說明本發明。本發明之遮蔽性膜係藉由在聚醯胺樹脂中摻配一定量之遮蔽材而得到。在本發明之遮蔽性膜中，作為聚醯胺樹脂之例子者，可列舉如：尼龍6、尼龍⑽、尼龍46、尼龍69、尼龍610、尼龍612、尼龍1卜尼龍12、聚己二醯間笨二甲胺（尼龍 MXD6)、及此等之混合物或共聚物或複合體等。尤其，在生產性和性能面上，以成本效益優異之尼龍6為佳。聚醯胺樹脂亦可以為了在熔融時抑制單體之生成等目的而經末端封閉。作為末端封閉劑者’可以使用：有機縮水甘油趟、二㈣野、安息香酸等單紐、二胺等。聚醯胺樹脂的相對黏度，並無特別限定。但以使用g⑽ 硫酸作為溶劑，在溫度25°C '濃度lg/dl之條件下測定之相對黏度為1. 5至5. 0為佳。較佳是2· 5至4. 5，更佳者疋在3· 0至4.0之範圍。相對黏度不滿丨· 5時，薄膜之力學特性容㈣著下降。相對黏度超過5.㈣，容之製膜性造成阻礙。、在聚臨胺樹脂中，因應必要，在不會對薄膜性能造成 =佳影響之範圍内，可以添加除了遮蔽材料以外之顏料、抗氧化劑、紫外線吸收劑、防腐劑、抗靜電劑、抗結塊劑、無機微粒子等各種添加劑中之丨種或2種類以上者。在聚醯胺樹脂中，亦可以為了提高薄膜之滑動性之目的而以摻配有潤滑劑。作為潤滑劑者，可以使用無機李潤滑劑、有機系潤滑劑之任一者。作為潤滑劑之具體例者= 321749 8 201037023 可以列舉如：黏土、滑石、碳酸鈣、碳酸鋅、矽灰石 (wollastonite)、氧化矽、氧化鋁、氧化鎂、矽酸鈣、鋁酸納、鋁酸i弓、紹;ε夕酸鎂、玻璃小球（glass baiι〇οη)、碳黑、氧化鋅、二氧化銻、彿石、水滑石（hydrotalcite)、層狀矽酸鹽、雙硬脂醯乙二胺等。其中也以氧化矽為佳。聚酿胺樹脂中之潤滑劑含量，以〇. 〇1至〇. 3質量％之範圍為適當。〇在本發明之遮蔽性膜中含有遮蔽材。作為遮蔽材者可以列舉如：氧化鈦、硫酸鋇、氧化鋅、硫化鋅、碳酸鈣等。其中以氧化鈦為佳。其原因在於氧化鈦在上述遮蔽材中彎曲率最高’在聚醯胺樹脂中含有時’少量即可得到高的遮蔽性。在遮敝材為氧化鈦之情形’其含量以5至40質量％為佳，尤其以15至30質量％為特佳。氧化鈦之含量不到5質量％時，薄膜之遮蔽度變成不〇到0.3，得不到如後述之充分遮光性。另—方面，超過4〇質量％時，除了機械物性下降之外，在延伸之時破裂之頻率變高，生產性容易下降。所含之氧化鈦的粒子種類並無特別之限定，不限定是銳鈦礦Unatase)型、金紅石（rutiie)型、Bruker nght 型等之任何一種。但是，從提高遮蔽性之觀點而言，以金紅石型氧化鈦為佳。士已知氧化鈦具有光活性作用。詳細而言，照射紫外線時在氧化鈦粒子之表面會產生自由基。此自由基進入聚合 321749 201037023 物基材中時，會發生聚合鏈之分解，而成為薄膜變黃的主要原因。因此，氧化鈦粒子以經實施表面處理者為佳。表面處理有無機處理與有機處理。作為無機處理者，有氧化鋁處理、氧化矽處理、氧化鈦處理、氧化锆處理、氧化錫處理、氧化銻處理、氧化辞處理等，其中也以氧化鋁處理為佳。有機處理者可列舉如使用：季戊四醇、三羥曱基丙烷等多元醇；三乙醇胺、三羥曱基胺等胺系；矽氧樹脂、烷基氯矽烷等矽氧系的處理劑之處理。氧化鈦之粒徑並無特別限定，但以平均粒徑為0.1至 0.5//m之範圍為佳，較佳是0.2至0.4# m之範圍。平均粒徑不到0. 1 // m時，在聚醯胺樹脂中之分散性差，粗大凝聚物係在薄膜中分散，在薄膜中產生針孔導致其價值下降。另一方面，平均粒徑超過0. 5/zm時，在將聚醯胺樹脂層製膜時，薄膜破裂之頻率變高，而導致生產性會有下降之傾向。在聚醯胺樹脂中摻配氧化鈦之方法，並無特別之限定者，可在製造步驟之任意時點中摻配。列舉例如，在聚醯胺樹脂聚合時添加氧化鈦之方法、在聚醢胺樹脂中高濃度混煉摻配氧化鈦製造母料後將其添加到聚醯胺樹脂中稀釋之方法（母料法；master batch)、將聚醯胺樹脂與氧化鈦在擠壓機中熔融混合之方法等。本發明中，以採用使用母料法在薄膜化前調整成所期望之氧化鈦濃度之方法為佳。 10 321749 201037023 本發明之遮蔽性膜的遮蔽度，必須為0. 3以上，以在 .〇. 4以上為佳，更佳是在0. 5以上。遮蔽度不到〇. 3時， -因為遮光性及遮蔽性變得不足，導致含油脂等之内容物容易氧化變差，且内容物因透明而可以看得見，故不佳。為了使薄膜之遮蔽度成為〇. 3以上，只要在本發明規定之範圍内調整氧化鈦含量，同時調整遮蔽性膜的厚度就可以。本發明中，遮蔽度是指藉由光學濃度計測定之光學濃 ❹度（O.D.)之意。此值愈大則遮蔽性愈高。本發明之遮蔽性膜以白色度為65至1〇〇%為佳。較佳疋75至100%，特佳是85至1〇〇%。白色度不足65%時，由於白色性不充分，故如包裝材料之要求有創新性之用途中商品價值恐怕會下降。本發明中，白色度是指使用曰本電色工業公司製的分光式色差計SE_6〇〇〇，依反射法，爪 28729之試驗方法測定試料之白色度而得值。白色度是可以從表示色之3刺激值的L*a*b木值的L*值來求得。薄 ◎膜之白色度可藉㈣膜之厚度、作為遮蔽義氧化欽之含量來調整。本發明之遮蔽性膜的抗張強度Μ在⑽胸以上為 L較佳是在⑽至22GMPa。抗張強度不到⑽胸時抑強分’穿刺強度有變差之傾向。該薄膜之抗張仗與抗張強度相同觀點來看，以在繼以上為佳，更佳疋在90至120%。本發明之遮蔽性膜的厚度，可以因應必或作為目的的機械強度'或作遮敝度次作為目的的白色度等而適當地 321749 11 201037023 選擇。薄難應作為包裝择作之以了力μ錢械強度和操作之今易度賴而言，以心，至3Gajd為佳，較佳是膜厚不到10_時，就得不到充分的機械強度㈣強度有變差之傾向。製作積層體時之總厚度’ 從同樣理由來看，以在10#m至30#m為佳，更佳 m至30仁m。本發明之遮蔽性膜，可以良好地作為容易製膜的單層薄膜使用。另一方面，在含有氧化鈦1〇至6〇質量％含有聚醯胺樹脂40至90質量％之白色層（A)的至少單面上積層不含氧化鈦之聚醯胺樹脂層（B)而製作成複數層薄膜，與單層薄膜相比，可得到高的遮蔽性，並且也可以提高機械物性，尤其可以提面穿刺強度。白色層（A)與聚酿胺樹脂層（b)分別亦可以複數存在。作成複數層薄膜時，單數或是複數之白色層（A)與單數或是複數之聚醯胺層（B)之厚度結構，當（A)層之合計厚度（厚度1)與（B)層之合计厚度（厚度2)的比率為（厚度 2)/(厚度1) = 1/4至3/1時，容易調整遮蔽性等物性，又可具有充分之機械物性。作成複數層薄膜時之層結構，可以考慮為在白色層（A) 之外層配置聚醯胺層（B)的（B)/(A)等之2種2層、或 (A)/(B)/(A)等之 2 種 3 層、或（B)/(A)/(B)/(AV(B)等之 2種5層等。其中，宜為在外層配置聚醯胺層之（B)/(A)/(B) 的2種3層。其原因為，與多層薄膜相比，厚度控制較簡單，並且機械物性等之平衡良好。 12 321749 201037023 有複數層薄膜時，藉由將聚醯胺層（B)作為外層，可以防止氧化鈦在薄膜表面滲出，並且可能使表面具有平滑性。藉此，聚醯胺樹脂不會失去本來具有之印刷適性、半調特性，而可以得到積層體。有複數層薄膜時，白色層（A)之氧化鈦含量是以10至 60質量％為佳，較佳是20至50質量％。氧化鈦之含量不到 10質量％時，在作成複數層薄膜時，很難使氧化鈦之含量 0成為5質量％以上，而不易得到充分之遮蔽度。另一方面，超過60質量％時，使多層結構之薄膜延伸時，破裂頻率變高，生產性容易下降。有複數層薄膜時，該複數層薄膜之氧化鈦含有率以在 40質量％以下為佳，更佳是5至40質量％。氧化鈦之含量不到5質量％時，不易得到充分之遮蔽度。另一方面，超過 40質量％時，除了機械物性下降之外，尚有延伸之時破裂頻率變高，生產性容易下降。 Ο 作成複數層薄膜時，聚醯胺層（B)中，亦可為了提高薄膜之手撕裂性等之目的而摻配有芳香族聚醯胺樹脂。芳香族聚醯胺樹脂只要是在與脂肪族聚醯胺摻配之際作成海島結構，並以芳香族聚醯胺樹脂作為島成分就可以，而無特別限制，可以使用由苯二甲胺與碳數6至12之α, ω-脂肪族二羧酸所組成之聚醯胺結構單元在分子鏈中含有 70莫耳％以上之樹脂等。具體上，可列舉如：聚己二醯間苯二甲胺、聚庚二醯間苯二曱胺、聚壬二醯間苯二甲胺、聚壬二醯對苯二曱胺、聚癸二醯對苯二甲胺等均聚物、己 13 321749 201037023 二醯間苯二曱胺/己二醯對苯二甲胺共聚物、庚二醯間苯二甲胺/庚二醯對苯二甲胺共聚物、壬二醯間苯二甲胺/壬二醯對苯二甲胺共聚物、癸二醯間苯二曱胺/癸二醯對苯二曱胺共聚物等共聚物，但從強度等基本特性優且工業上比較容易得到之觀點而言，以己二醯聚間苯二甲胺為佳。複數層薄膜中，在聚醯胺層（B)摻配芳香族聚醯胺樹脂時，聚醯胺層（B)之芳香族聚醯胺樹脂含量是以在5至 30質量％之範圍為適當。芳香族聚醯胺樹脂之含量少於5 質量％時，則直線切割性之發現不足，超過30質量°/◦時，則薄膜之強度特性會下降。複數層薄膜以穿刺強度在7. 5N以上為佳，更佳是在 8. 5N以上。穿刺強度不到7. 5N時，則供應包裝用途時，因為耐穿刺性不足，故點心，尤其是，在如馬鈴薯片等容易有堅硬銳利角之點心中，藉由製袋機或包裝機填充時恐怕會有針孔之產生。為了使穿刺強度成為7. 5 N以上，則必需要調整氧化鈦之含量、含有氧化鈦層、與不含有氧化鈦層之厚度結構。本發明之遮蔽性膜可以藉由以下之方法等來製造。例如，將加有氧化鈦之聚醯胺樹脂在擠壓機内加熱熔融並從T壓模擠壓成薄膜狀，利用公知的氣刀鑄模法、施加靜電鑄模法等澆鑄法在旋轉之冷卻桶上冷卻硬化後，製造成未延伸薄膜，對該未延伸薄膜實施延伸處理，就可以製造。本發明之遮蔽性膜，為了保有充分之強度或穿刺強度，以延伸薄膜為宜。延伸前之薄膜經定向時，因為在後 14 321749 201037023 .步驟中延伸性會下降，故延伸前之薄無定向之狀態為佳。作成複數層薄膜之、二:，=、樣之處理而製造。、寺也可以貫施同 * 延伸薄膜之延伸倍率，在為佳。縱橫雙軸延伸時，以㈣^伸時是以L 5倍以上通常面積倍率為3倍《上倍以上為佳，至13倍。設在此範圍則可 1倍為佳’更佳是6. 5 ^ ㈣延伸處理步驟之_ /機械物性之薄膜。 Ο '專膜’在進行延伸處理之拉幅s (tenter)内於150至220。。^ “ 拉巾田盗於0至10%，較佳是在2至錢u應需要方向之鬆弛處理。 6/°之乾圍，貫施縱方向及/或橫為了降低所得遮蔽性臈之熱間之溫度及時間最適化，> 〜也且在比熱固定處理之最高溫度還低的溫度中進行熱鬆弛處理。薄膜之L伸方法’雖無特別限定，但以同時雙韩延伸 0方法為佳。適用同時雙轴延伸方法時，-般可以使薄膜兼備有機械特性、光學特性、熱尺寸安定性、财針孔性等實用特!生適口同時雙轴延伸方法之其他理由，可列舉如，在縱向延伸之後進行橫向延伸之逐次雙軸延伸方法中，由於在縱向延伸時進行薄膜之定向結晶化後，橫向延伸時之聚醯胺樹脂的延伸性會下降，導致在氧化鈦濃度高時薄膜之破裂頻率有變高之傾向。又軸疋向聚ik私系樹脂薄膜與雙軸定向聚酯系樹脂 4膜相比％c則尺寸安定性較差。因此，一般作為包裝袋使 15 321749 201037023 用之際會發生卷曲現象，自動填充裝置不能正確地抓住袋而使袋口打開，導致食品等内容物會有洩漏之問題。如此現象係在縱向延伸之後改成橫向延伸製造之逐次雙軸延伸法中非常顯著地出現。因此，由於此卷曲現象是沿著薄膜之寬度方向愈靠端部則變得愈大，使在薄膜端部與接近中心部對半折之包裝袋，會產生收縮率差異，因為袋之表面尺寸與背面尺寸不同，而發生卷曲現象。為了抑制該卷曲現象，期望採用可以製造在寬度方向有均勻物性之薄膜的所謂之抑制彎曲（bowing)的薄膜之同時雙軸延伸方法。在如此得到之單層或複數層之薄膜中，因應需要，也以實施電暈放電處理等表面處理為佳。上述之薄膜是可以適合作為用以構成包裝材料之素材使用。例如，在薄膜上配置密封劑層（Z)後熱密封，可以構成袋狀體，或是作為盤狀（tray)包裝之蓋材等使用。袋之形態可列舉如：三面密封袋、四面密封袋、枕頭袋、自立袋、火箭型包裝等。作為使用薄膜之包裝材料者，可列舉如用於：飲食品、水果、果汁、飲料水、酒、調理食品、水產製品、冷凍食品、肉製品、燉煮物、年糕、液體湯汁、調味料、其他等之各種飲食品等、液體清潔劑、化妝品、化成品等内容物的填充包裝材。如此之薄膜尤其是由具有高穿刺強度並且不使用鋁箔之薄膜所構成，所以在微波爐調理之高溫殺菌食品中可以發揮效果。說明本發明之遮蔽性積層體。 16 321749 201037023 本發月之遮蔽&積層體至少是由租隔樹脂層⑴/聚酿胺ΐ脂層⑺/密_層⑴等3層所構成的料體。如此之積層體通常是積層⑴、（γ)、⑺各層之胺樹脂層⑺是由上述之單層或複數層的遮紐膜所構成。說明在聚酿胺樹月旨層⑺中可以摻配之潤滑劑。2 == 層且含有氧化欽時，或為複數層且在外層 Ο 置3有氧化鈦之層時，氧化鈦是渗出至聚醯胺樹脂層⑺ 之表層，即使沒有添加潤滑劑，氧化鈦也㈣有潤㈣之作用。因此不㈣獅加潤龍。但是添加也不妨害。並且在複數層之情形，在外層設置不含氧化鈦之聚ϋ胺樹脂層時，以在該層添加上述之潤滑劑為佳。在構成本發明之遮蔽性積層體的聚醯胺樹脂層，含有作為遮蔽材之氧化欽的情形中，其含量在聚酸胺樹脂層⑺ 中必須為5至40質量％範圍，而以15至3〇質量％為佳。氧化鈦之含量不到5質量％時，遮蔽性積層體之遮蔽度不到〇〇. 3，該情形就得不到後述之充分遮光性，結果，包裝食品時，内容物容易發生經時氧化劣化現象。另—方面，超過 4〇質量％時，在延伸聚醯胺樹脂時，破裂頻率變高、導致生產性下降。構成聚醯胺樹脂層（γ)之薄膜，可以藉由與上述之遮蔽性膜同樣的方法製造。此時，聚醯胺樹脂薄膜之延伸方法並無特別限定，如上述以同時雙軸延伸法為佳。可以逐次雙軸延伸之鈦含量上限是受層厚度或延伸倍率支配’大致上，單層薄膜時是 321749 201037023 30質量％左右，複數層薄膜時是35質量％左右。因此本發明中，以制可以在更叙氧化鈦含量朗巾進行雙轴^ 伸的同時雙轴延伸法為佳。在聚酿胺樹脂層⑺中，為了改善與構成積層體之1 他2層’即，阻隔樹脂層〇〇及密封劑層⑺的密著性，^ 對單面或兩面實施易接著皮膜處理為佳。為了該處理，、雨常使用如胺醋樹脂、胺醋/脲樹脂之成分之二為至7.0/zm左右的皮膜。、$成尽度 ^本發明之箱性積層體巾，阻隔龍層（並無特別限定。例如，可以使用如：在員金屬氧化物之薄膜(_);在基材薄膜表面=鐘氣乙雜歡）等具有氣―之樹脂塗膜㈣膜涛膜），積層聚己二醯間苯二甲胺（Nyl〇nMXD6)或乙稀乙稀醇共聚物⑽H)等阻隔性樹脂的薄膜（積層薄膜）等。阻隔樹脂層⑴也可以在聚酿胺樹脂層⑺中之盘密封劑層之積層面相反面形成氣體阻隔塗膜層。作為形成氣體阻隔塗膜層之樹脂者，可列舉如：pVDC、聚乙烯醇 (PVA)、EVOH、％i〇nMXD6、或是此等之改質體等顯現阻隔性之樹脂等。但是，並無特別限定者。作為構成阻隔樹脂層（X)之材料者，從阻隔氧氣性及阻隔水蒸氣性之觀點而言，較佳者是以蒸鍍金屬氧化物之薄膜（蒸鍍薄膜）為佳。在阻隔樹脂層（X)中使用之基材薄膜，以藉由聚烯煙乐樹脂、聚醯胺樹脂、聚對苯二曱酸乙二酯樹脂（ΡΕγ)、聚 321749 18 201037023 萘二甲酸乙二酯樹脂等所形成的薄膜為佳，尤其在成本、耐熱性之觀點上，以聚對苯二曱酸乙二酯樹脂等聚酯薄膜、聚乙烯或聚丙烯等聚烯烴薄膜為佳。基材薄膜亦可以是無延伸性薄膜、單軸延伸薄膜、雙轴延伸薄膜之任一種，但從尺寸安定性及機械特性之觀點，以雙軸延伸薄膜為特佳。蒸鍍薄膜之蒸鍍層，可以使用鋁'矽、鋅、鎂等之氧化物為宜。其中，從氧氣阻隔性能及水蒸氣阻隔性能及成 0本面而言，使用氧化銘為更佳。金屬氧化物可以是前述之單獨者，也可以是混合複數者，亦可以為殘留一部分金屬成分者。蒸鑛層為金屬氧化物之情形，由於該金屬氧化物是完全氧化物，是以該蒸鍍層為完全透明甚佳，但是，通常形成完全氧化物時，形成過剩氧化部分之機率高，該部分之氣體阻隔性能會變差，就全體而言，很難得到高的阻隔性能。因此，亦可以是有些金屬成分殘留之不完全氧化膜。 Ο蒸鍍薄膜之光線穿透率，以70%以上為佳，較佳是80°/〇以上，更佳是85%以上。蒸鍍薄膜之光線穿透率不到70%時，是有比較多之金屬成分殘留在蒸鍍層的狀態，尤其使用紹作為蒸鍍材料之情形，使用微波爐時容易產生火花。本發明之遮蔽性積層體中，為了賦予必要之氧氣阻隔性，阻隔樹脂層（X)之氧氣穿透度是以0至100ml/(m2 · day · MPa)為佳，較佳是 0 至 50inl/(m2 · day · MPa)，更佳是 0 至 20ml/(m2 · day · MPa)。本發明之遮蔽性積層體中，為了賦予必要之水蒸氣阻 19 321749 201037023 隔性’阻隔樹脂層（X)之水蒸氣穿透度是以〇至1 〇〇g/ (m2 _ day)為佳’較佳是0至50g/(m2.day)，更佳是ο至2〇g/(m2· day)。可以作為阻隔樹脂層（X)使用之市售蒸錄薄膜者，可以列舉如：Toray Film加工公司製之VM~PET 1011HG-CR(基材薄膜·· PET，蒸鍍層··氧化銘）、Tohcel 1〇公司製之HP-BR (基材薄膜：PET ’蒸鑛層：氧化銘）、三菱樹脂公司製之 Techbarrier T(基材薄膜：PET，蒸鍍層：氧化矽）、東洋紡績公司製之ECOSYAR VE100(基材薄膜：PET，蒸鐘層：陶究）、尾池工業公司製之M0S-TR(基材薄膜：pet，蒸鍵層：氧化矽系）等。可以作為阻隔樹脂層（X)使用之市售塗佈薄膜者，可以列舉如：由尼帝佳公司製之Emblem DC DCR-15(基材薄膜·尼龍6 ’塗佈層：PVDC)、由尼帝佳公司製之Einblet DC KPT- 15 (基材薄膜：PET，塗佈層：PVDC)、由尼帝佳公司製之Sevix Y0P-15C基材薄膜：尼龍6，塗佈層：PVA系+ 層狀矽酸鹽）、由尼帝佳公司製之Emblem NV-15(基材薄膜，尼龍6，塗佈層：多元醇系聚合物+多叛酸系聚合物）等。可以作為阻隔樹脂層（X)使用之市售積層薄膜者，可以列舉如：由尼帝佳公司製之Emblon M Ml00-15(基材薄膜：複數層MXD 6系）、由尼帝佳公司製之EmblonEE301~i5 (基材薄膜：複數層EV0H系）等。本發明之遮蔽性積層體中，作為構成密封劑層（Z)之 20 321749 201037023 樹脂者，可以使用：低密度聚乙稀、中密度聚乙烯、高密度聚乙烯、直鏈狀聚乙烯'聚丙烯、聚乙烯/聚丙烯共聚物、乙缚一醋酸乙烯酯共聚物、離子I合物（Ionomer)樹脂、乙烯一丙烯酸/甲基丙烯酸共聚物、乙烯〜丙烯酸/甲基丙烯酸酯共聚物、聚醋酸乙烯醋系酷樹脂等。此等可以單獨使用，亦可以使用與其他樹脂或成分共聚合或熔融混合者，又亦可實施酸改質等。亦可以使用多〇層之前述樹脂成分。尤其特佳者是熱密封強度或材質本身之強度高之聚乙烯、聚丙烯、聚乙烯/聚丙烯共聚物等聚埽烴樹脂。形成密封劑層（Z)之方法’可列舉如：在由前述密封劑樹脂所成之薄膜或薄片經由接著劑積層聚醯胺樹脂層（γ) 的方法、將密封劑樹脂溶融擠壓在聚酿胺樹脂層（Y)上之掩壓積層方法、將聚醯胺樹脂層（Y)與密封劑層同時擠壓積層之共擠壓出方法、在聚酿胺樹脂層（Y)上用塗膜機塗佈用以〇形成密封劑層之樹脂的方法等。在由密封劑樹脂作成薄膜或薄片之情形’該薄膜或薄片可以是未延伸狀態，亦可以是低倍率之延伸狀態’但實際使用上較佳是在未延伸之狀態。密封劑樹脂薄膜或薄片之形成方法，可以使用如：在擠壓機中加熱、溶融並從]'壓模機壓出後，用冷卻輥筒等冷卻硬化之拉幅機法，或是藉由圓形壓模機擠壓後，藉由水冷或空氣冷卻使冷卻硬化之管狀（tubular)法。逸、封劑層（Z)之厚度並無特別限定，而以20至100# m 為隹’以40至70#!!)為更佳。 21 321749 201037023 本發明之遮蔽性積層體的遮蔽度必須在〇. 3以上，較佳是在0.4以上，更佳是在〇·5以上。遮蔽度不到〇 3時，由於遮光性及遮蔽性變得不充分，以該積層體包裝時’含有油脂等之内容物容易氧化劣化，又，亦可能因為包裝材透明導致内容物可以看得到，因而不佳。為了使積層體的遮敝度成為〇. 3以上之範圍，則在積層體使用之聚醯胺樹脂層（Υ)中，調整氧化鈦等遮蔽材之含量，並且調整聚醯胺樹脂層（Υ)的厚度。本發明之遮蔽性積層體使用氧化鈦等白色系遮蔽材的情形，其白色度以在60至100%為佳。以在65至1〇0% 較佳，更佳是在70至100%，特佳是在8〇至丨〇〇%。白色度不到60%時，由於白色性不充分，在像包裝材料之要求創新性用途方面恐性會降低商品價值。同時，積層體之白色度是利用前述方法測定。積層體之白色度，可以藉由聚醯胺樹脂層（Υ)的厚度與氧化鈦含量來調整。本發明之遮蔽性積層體的氧氣穿透度，必須在 1〇〇ml/(m2 · day · MPa)以下，而以在 7〇mi/(m2 · day · Mpa) 以下為佳，以在3〇ml/(m2 · day · MPa)以下更佳。氧氣穿透度比100ml/(m · day · MPa)高時，經製袋加工後的k子之氣體阻隔性變得不足，内容物容易氧化劣化。本發明之遮蔽性積層體的水蒸氣穿透度，要求必需在 1〇〇g/(ro · day)以下為佳，水蒸氣穿透度大於1〇〇g/(m2 · •，水分減量不能忽視，内容物乾燥而商品價值有降低之情形。因此，以在50g/(m2.day)以下較佳，以在 321749 22 201037023 20g/(m2 · day)以下更佳。作為本發明之遮蔽性積層體之耐針孔性者，以在20 °C環境下經過5000次重覆彎曲疲勞測試中之針孔的產生個數在2 0個以下為佳。更佳是在10個以下。針孔之產生個數超過20個時，積層體作為包裝材使用時，商品等在運送之際積層體可能會產生孔洞。本發明之遮蔽性積層體可以適合作為包裝材料使用。 0例如：將密封劑層（Z)熱密封，可以作成袋狀體、或盤狀包 ' 裝之蓋材等之包裝體使用。袋的形態可以列舉如：三面密封袋、四面密封袋、枕頭袋、自立袋、火箭型包裝等。使用本發明之遮蔽性積層體的包裝材料，可以填充包裝如：水果、果汁、飲料水、酒、調理食品、水產製品、冷凍食品、肉製品、燉煮物、年糕、湯汁、調味料等各種飲食品等；液體清潔劑；化妝品；化成品等内容物。尤其適合含有容易受到氧化劣化影響之油脂之製品的包裝，可 Ο以在商店陳列時曝露於太陽光或螢光燈光之條件下，發揮效果。 (實施例）以下，藉由實施例更具體說明本發明，但是，本發明並不侷限於此等實施例。 1.測定方法下述項目（1)至（6)的測定是對於在23°C、50% RH之環境下放置2小時以上之試料，於23°C、50%RH之條件下實施。 23 321749 201037023 » (1) 各層之厚度藉由掃描型電子顯微鏡（SEM)進行薄膜剖面之觀察，測定各層之厚度。 (2) 無機粒子之粒徑利用島津製作所公司製之雷射繞射散射式粒徑測定機 SALD-2000 測定。 (3) 白色度利用分光式色差計SE-6000(曰本電色工業公司製），求取作為色調L*。 (4) 遮蔽度以利用馬克貝斯公司夕 < 只社）製光學濃度計 TR932並使用直徑3 mm之穿透噴嘴所測定之光濃度（〇. D.) 當作遮蔽度。 (5) 穿刺強度將薄膜以不使其鬆弛的方式貼在直徑4〇min之環（ring) 上’使用尖端角度60度、尖端彎曲半徑為〇.丨龍之藍寶石製針，以50imn/分鐘之速度穿刺由環形成之圓的中央之薄膜的部分，將針貫通時之力量換算成薄膜厚度lmm，當作穿刺強度。 (6 )遮蔽性膜之延伸性在經由將聚酿胺樹脂層延伸而製作⑽⑽薄膜之中間，將發生破裂之次數不到2次的情形評估為延伸性「良好」，將2次以上之情形評估為延伸性「不良。 (7)抗張強度 <」° 321749 24 201037023 使用島津製作所公司製之DSS-500型繪圖機’依ASTM D882測定，以MD方向、TD方向之平均值來評估。 (8) 抗張伸度使用島津製作所公司製之DSS-500型繪圖機，依ASTM D882測定，以MD方向、TD方向之平均值來評估。 (9) 氧氣穿透度使用莫孔公司（乇>社）製之氧氣阻隔測定器 (OX-TRAN2/20) ’在溫度20°C、相對濕度65%之環境下測定氧氣穿透度[ml/(m2 · day · MPa)]。 (10) 水蒸氣穿透度依據JIS K-7129記載之方法’在溫度4(TC、濕度90% RH中’藉由莫孔公司製之PERMATRAN-W1測定水蒸氣穿透度[g/(m2 · day)]。 (11) 耐針孔性將MD300mmxTD200mm大小之薄片狀積層體試樣弄圖而 Ο握持成直徑89mm(3. 5英吋）之圓筒狀，使沿著圓筒之長度方向之初期握持間隔成為178min(7英吋），使最大彎曲時之握持間隔成為25mm(l英吋），以格魯博試驗機（夂儿求于只少-）（理學工業公司製）在2(rcx65% RH環境下進行$ 次彎曲，其後計算針孔數而評估。 (12)遮蔽性積層體之延伸性在製作聚醯胺樹脂層1〇萬每角m 4膜之期間’將發將2 裂之次數不到2次的情形是坪估為延伸性「良好次以上之情形是評估為延伸性「不_ 义」 321749 25 201037023 2.原料在下述實施例、比較例中使用之原料如以下所述。 (1)尼龍6樹脂（Ny6) 由尼帝佳公司製A1030BRF，相對黏度3. 0 (2) 聚己二醯間苯二曱胺（NXD6) 三菱瓦斯化學公司製MX尼龍6〇〇7，相對黏度2.6 (3) 鈇母料在40質量份尼龍6樹脂中，乾摻配60質量份之紅寶石型平均粒徑〇. 4// m的氧化鈦（a)(鈦工業公司製，KRONOS 氧化鈇1074)。將此摻配物用設定溫度250X：之直徑30 mm 圓筒雙軸擠壓機熔融混煉，擠壓成直線狀，經冷卻、硬化後，切斷，得到顆粒形狀之鈦母料（a)。在40貝量份尼龍6樹脂中，乾摻配質量份之紅寶石3L平均粒彳空〇. 35 // m的氧化鈦（b)(鈦工業公司製， Ki^NOS氧化鈦KR_3⑻。將此換配物用設定溫度之直徑3Gmm圓筒雙軸㈣機㈣混煉，_成纽狀，經冷斷’得到顆粒形狀之鈦母料⑸。富士 Silysia公司、之氧化矽微粒子(SyiysiaSlOP: 在此溫度下1拌麻均粒徑U心），維持在100°c，面授拌-面加奴到26^應系統内成為均句為止。接著一再花費1小時釋放m維持在L5MPa之壓力1小時， ’釋放[力到成為常壓為止，再進行聚H、時。 321749 26 201037023 在聚合結束之時間點’反應生成物倒出成直線狀，經冷卻、硬化後’切斷，得到由聚醯胺樹脂所成之顆粒。其次，將顧粒在95 c之熱水中精煉8小時除去未反應單體等，之後加=乾燥。所付氧切母料之相對黏度為，二氧化石夕含量是6質量％。 (實施例1) 〇〇摻配尼龍6樹脂（_與鈦母料⑷，如表m示使氧201037023 . . . 6. Technical Field of the Invention The present invention relates to a masking film and a shielding layered body using the film, for example, a masking film which can be used as various food packaging materials, particularly as an inner layer of a bag. A shielding layered body of the film was used. [Prior Art] As a thermoplastic film which imparts shielding properties, it is known that a resin containing a large amount of a pigment such as inorganic particles or organic particles is laminated on the surface of a thermoplastic film or a pigment is directly added to a thermoplastic resin. For example, Japanese Patent Publication No. 11-34205A discloses a packaging material comprising a white first printing layer and a second printing layer having a high light-shielding color, and a packaging material having a colored resin layer. Or use the packaging materials of both, and make the total light transmittance to be 30% or less. However, in the case where the colored resin layer is provided, the first printed layer and the second printed layer which are the plurality of layers of the printing ink layer are provided, although the light-shielding property and the shielding property are obtained, in order to provide the light-shielding property, it is necessary to provide one layer. The new resin layer causes problems in terms of manufacturing steps or costs. A pigment film is directly added to a thermoplastic resin to form a thermoplastic film. For example, JP2001-1 1210A discloses a white film in which an inorganic substance such as titanium oxide or calcium carbonate is added to a polyester resin. However, the obtained polycrystalline film can impart whiteness, but it cannot be made low in specific gravity, and the film becomes too hard, which is difficult to apply to various food packaging materials requiring impact resistance and bending fatigue resistance. On the other hand, as a packaging material, a laminate having at least two layers of a nylon film 3 321749 201037023 layer and a sealed grease film layer is known. The nylon film layer is mainly used to prevent the impact from being transmitted or the layer of the pinhole or the bag which is broken due to friction with the contents. The sealant resin film layer is a layer formed of a polyolefin resin such as polyethylene or polypropylene for heat-sealing the packaging material. In a packaged product such as packaged food, the contents are easily deteriorated. For example, the monthly scorpion is reported in foods such as snacks, chocolate, peanuts, and fry, and Renbao Valley is susceptible to deterioration or deterioration due to the influence of light or oxygen. Therefore, the package I' of the food containing fats and oils needs to have a shielding property for sufficient light shielding and an oxygen barrier property for replacing the package for gas for deoxidation. As a packaging material excellent in shielding property and oxygen barrier property, in addition to the above two layers of the nylon film layer and the sealant resin film layer, a film which is laminated and inlaid is known. However, the packaging material of (4) is used when it is inspected and mixed with metal pieces (foreign materials) of the contents using a metal detector or the like! Lu will react with the metal detector, and it is difficult to detect the metal piece (foreign matter) into the #'. Because it is heated by the microwave oven, it will generate sparks from the box. Therefore, there is also a problem that it is not suitable for the microwave oven. Therefore, dealumination has become a topic in the food packaging industry. In the case of using a transparent vapor-deposited film as an oxygen barrier layer, it is known that the surface property is improved (4) White =: 3 layers of a transparent vapor-deposited Nilan film/white sealant layer are formed. The laminate may have a certain degree of light blocking property and shielding property. :: Two = points. Because the sealant layer is directly in contact with food, the titanium oxide doped with the layer will absorb the food oil. As a result, the sealant part of the inner surface of the bag will accumulate like grapefruit skin and the so-called " Pomelo 321749 4 201037023 · « . The problem of damage to the quality of packaging materials. Then, as a packaging material which does not use titanium in the sealant layer which is in direct contact with the content, a light-shielding laminated body in which a continuous printing film is provided by printing ink is disclosed in JP 10-305513 A. Further, as described above, in JP 11-34205 A, a packaging material in which a printing layer and a colored resin layer are simultaneously provided is disclosed. SUMMARY OF THE INVENTION (Problem to be Solved by the Invention) An object of the present invention is to provide impact resistance and bending fatigue resistance which are required for various food packaging materials, and the manufacturing steps are not simplified, and the manufacturing cost is not increased, and the puncture strength is increased. A masking film that is excellent in shielding properties and light-shielding properties and can be heated in a microwave oven due to aluminum less. (Means for Solving the Problem) As a result of intensive research, the present inventors have found that a certain amount of the masking material is contained in the polyamide resin, and the above problems can be solved, and the invention is completed. That is, the present invention relates to the following (1) to (14). (1) A masking film characterized by containing a masking material and a polyamide resin, and the shielding degree is 0. 3 or less. (2) The masking film of (1), wherein the masking material is a white masking material having a whiteness of 65 to 100%. (3) A masking film according to (2), which contains 5 to 40% by mass of titanium oxide and 60 to 95% by mass of polyamine resin. (4) A masking film according to (2) which is laminated on at least one side of a first layer containing titanium oxide 10 to 60 mass 5 321 749 201037023 Å/〇 and containing polyamine resin 40 to 90% by mass. A laminate having a second layer composed of a titanium oxide-free polyamide resin has a puncture strength of 7. 5 N or more. (5) The masking film according to any one of (2) to (4) wherein the main component of the polyamide resin is nylon 6. (6) The masking film according to any one of (2) to (5), wherein the masking film is simultaneously biaxially stretched. (7) A shielding layered product comprising a barrier resin film (X), a polyimide resin layer (Y) composed of the shielding film according to any one of the above (1) to (6), and a sealing layer Three layers of layers such as the agent layer (Z), the shielding degree is 0. 3 or more, the oxygen permeability is l〇〇ml/(m2·day·MPa) or less. (8) The shielding layered body according to (7), wherein the water vapor permeability is 100 g/(m2 · day) or less. (9) The shielding layered body according to any one of (7) to (8), wherein the number of pinholes generated when the bending fatigue test is repeated 5000 times in an environment of 20 ° C x 65% RH is 20 or less. (10) The masking laminate according to any one of (7) to (9), wherein the whiteness is from 60 to 100%. (11) A packaging material comprising the shielding layered product according to any one of the above (7) to (10). (Effect of the Invention) Since the masking film of the present invention contains a polyamic acid resin, it has high flexibility and can suppress the occurrence of pinholes. Therefore, when used as a packaging material, gas leakage or mixing can be minimized. According to the present invention, since 6 321749 201037023 = chemical == shielding, - (4), the layer and the absence of the vaporized titanium layer, the formation of mechanical properties including oxidation degree is further improved, and the tensile strength can be made. /Stabilization According to the product P _ of the masking enthalpy and the oxygen resistance m of the present invention, it is possible to provide a food having sufficient masking grease. Laminated body ° _ layer body, especially in the case of oil quality: when used, can suppress the content caused by oxidation (9) t month of the shielding layer, because it is not in the sealant layer but in the material amine tree layer Since titanium oxide is contained and the material is shielded, the contents are not directly in contact with the oxidized crystal in the package hex. Thus, the quality of the packaging material is not impaired by the so-called grapefruit peeling of the sealant layer, or the titanium is mixed into the contents. In the shielding layered product of the present invention, since the polyimide layer is used, the curvature is strong and the occurrence of pinholes can be suppressed. Therefore, when used as a packaging material, gas leakage or mixing can be minimized. The shielding layered body of the present invention has an oxygen barrier property and a water vapor barrier, and can be suitably used as a packaging material containing a moisture content. The shielding layered body of the present invention can be used without using an aluminum foil. It is a barrier property and an oxygen barrier property, so when it is used as a packaging material, foreign matter is inspected by a metal detector or heated by a microwave oven. [Embodiment] The best mode for carrying out the invention: 7 321 749 201037023 Hereinafter, the present invention will be described in detail. The masking film of the present invention is obtained by blending a certain amount of a masking material in a polyamide resin. In the masking film of the present invention, examples of the polyamide resin include nylon 6, nylon (10), nylon 46, nylon 69, nylon 610, nylon 612, nylon 1, nylon 12, and polyhexamethylene. M-xylylenediamine (nylon MXD6), and mixtures or copolymers or composites thereof. In particular, it is preferable to use nylon 6 which is cost-effective in terms of productivity and performance. The polyamide resin can also be blocked at the end for the purpose of suppressing the formation of a monomer during melting. As the terminal blocking agent, a mono-, diamine or the like such as organic glycidinium, di(tetra), benzoic acid or the like can be used. The relative viscosity of the polyamide resin is not particularly limited. However, the relative viscosity measured by using g(10) sulfuric acid as a solvent at a temperature of 25 ° C 'concentration lg / dl is 1. 5 to 5. 0 is better. Preferably it is 2·5 to 4. 5, better, 疋 at 3·0 to 4. The range of 0. When the relative viscosity is less than 丨·5, the mechanical properties of the film are reduced. Relative viscosity exceeds 5. (4) The film-forming property of the film is hindered. In the polyamine resin, if necessary, pigments, antioxidants, ultraviolet absorbers, preservatives, antistatic agents, anti-knots other than the masking material may be added within a range that does not have a good influence on the film properties. Among the various additives such as a bulking agent and inorganic fine particles, or two or more types thereof. In the polyamide resin, a lubricant may be blended for the purpose of improving the slidability of the film. As the lubricant, any of an inorganic plum lubricant and an organic lubricant can be used. Specific examples of the lubricant = 321749 8 201037023 For example: clay, talc, calcium carbonate, zinc carbonate, wollastonite, cerium oxide, aluminum oxide, magnesium oxide, calcium silicate, sodium aluminate, aluminum Acid i bow, Shao; magnesium oxalate, glass baiι〇οη, carbon black, zinc oxide, cerium oxide, buddha, hydrotalcite, layered citrate, double stearin Ethylenediamine and the like. Among them, cerium oxide is also preferred. The content of lubricant in the polyamine resin is 〇. 〇1 to 〇. The range of 3 mass% is appropriate.遮蔽 The masking material is contained in the masking film of the present invention. Examples of the masking material include titanium oxide, barium sulfate, zinc oxide, zinc sulfide, and calcium carbonate. Among them, titanium oxide is preferred. The reason for this is that titanium oxide has a high bending curvature in the above-mentioned masking material, and when it is contained in a polyimide resin, a small amount can provide high hiding property. In the case where the concealing material is titanium oxide, the content thereof is preferably 5 to 40% by mass, particularly preferably 15 to 30% by mass. When the content of the titanium oxide is less than 5% by mass, the degree of shielding of the film becomes zero. 3, sufficient light shielding properties as will be described later. On the other hand, when it exceeds 4 〇 mass%, in addition to the decrease in mechanical properties, the frequency of rupture increases when it is extended, and productivity is liable to lower. The type of the titanium oxide to be contained is not particularly limited, and is not limited to any one of an anatase type, a rutile type, and a Bruker nght type. However, from the viewpoint of improving the shielding property, rutile-type titanium oxide is preferred. It is known that titanium oxide has a photoactive action. Specifically, when ultraviolet rays are irradiated, radicals are generated on the surface of the titanium oxide particles. When this radical enters the polymerization of 321749 201037023, the decomposition of the polymer chain occurs, which becomes the main cause of yellowing of the film. Therefore, it is preferred that the titanium oxide particles are subjected to surface treatment. The surface treatment has inorganic treatment and organic treatment. As the inorganic processor, there are alumina treatment, cerium oxide treatment, titanium oxide treatment, zirconia treatment, tin oxide treatment, cerium oxide treatment, oxidation treatment, and the like, and it is preferable to treat it with alumina. The organic processor may be, for example, a polyol such as pentaerythritol or trihydroxydecylpropane; an amine such as triethanolamine or trihydroxydecylamine; or a treatment of an oxygen-based treating agent such as a decyloxy resin or an alkyl chlorodecane. The particle diameter of the titanium oxide is not particularly limited, but the average particle diameter is 0. 1 to 0. The range of 5//m is preferably, preferably 0. 2 to 0. 4# m range. The average particle size is less than 0. At 1 / m, the dispersibility in the polyamide resin is poor, and the coarse coagulum is dispersed in the film, and the occurrence of pinholes in the film causes the value thereof to decrease. On the other hand, the average particle size exceeds 0. At the time of 5/zm, when the polyimide resin layer is formed into a film, the frequency of film breakage becomes high, and productivity tends to decrease. The method of blending titanium oxide in the polyamide resin is not particularly limited and may be blended at any point in the production step. For example, a method in which titanium oxide is added during polymerization of a polyamide resin, a method in which a master batch is prepared by mixing a titanium oxide in a polyamine resin at a high concentration, and then added to a polyamide resin to be diluted (master batch method; Master batch), a method of melt-mixing a polyamide resin with titanium oxide in an extruder, and the like. In the present invention, a method of adjusting the desired titanium oxide concentration before the film formation by using the master batch method is preferred. 10 321749 201037023 The shielding degree of the shielding film of the present invention must be 0. 3 or more, in the . Hey. 4 or more is better, and more preferably it is 0. 5 or more. The degree of shadowing is less than 〇. At 3 o'clock, since the light-shielding property and the shielding property are insufficient, the contents containing oil and fat are easily oxidized, and the contents are visible because they are transparent, which is not preferable. In order to make the shielding degree of the film become 〇. In the case of 3 or more, the titanium oxide content may be adjusted within the range prescribed by the present invention, and the thickness of the shielding film may be adjusted. In the present invention, the degree of shielding refers to the optical concentration measured by an optical densitometer (O. D. ). The larger the value, the higher the shielding. The masking film of the present invention preferably has a whiteness of 65 to 1%. Preferably, it is from 75 to 100%, particularly preferably from 85 to 1%. When the whiteness is less than 65%, since the whiteness is insufficient, the value of the product may be lowered if the packaging material is required to be innovative. In the present invention, the whiteness is obtained by measuring the whiteness of the sample by a spectroscopic colorimeter SE_6, manufactured by Sakamoto Electric Co., Ltd., according to the reflection method and the test method of the claw 28729. The whiteness can be obtained from the L* value of the L*a*b wood value representing the 3 stimulus value. The whiteness of the film can be adjusted by the thickness of the film and the content of the mask. The tensile strength of the masking film of the present invention is preferably at (10) to 22 GMPa. When the tensile strength is less than (10), the puncture strength tends to be deteriorated. The film has the same tensile strength and tensile strength as the above, preferably in the above, more preferably in the range of 90 to 120%. The thickness of the masking film of the present invention can be appropriately selected according to the mechanical strength of the object or the intended whiteness of the degree of concealing, etc., 321749 11 201037023. Difficult to be used as a package to choose the strength of the force and the ease of operation, the heart, to 3Gajd is better, preferably when the film thickness is less than 10_, it will not be sufficient Mechanical strength (4) The tendency of strength to deteriorate. The total thickness at the time of producing the laminate is preferably from 10 #m to 30#m, more preferably from m to 30 lm, for the same reason. The masking film of the present invention can be suitably used as a single-layer film which is easy to form a film. On the other hand, a polyamine-containing resin layer (B) containing no titanium oxide is laminated on at least one side of a white layer (A) containing from 10 to 6 % by mass of titanium oxide and containing from 40 to 90% by mass of the polyamide resin. The film is formed into a plurality of layers, and a high hiding property can be obtained as compared with a single-layer film, and mechanical properties can be improved, and in particular, the puncture strength can be improved. The white layer (A) and the polyacrylamide resin layer (b) may also be present in plural. When forming a plurality of layers of film, the thickness of the singular or plural white layer (A) and the singular or plural polyamine layer (B), when the total thickness of the (A) layer (thickness 1) and (B) layer When the ratio of the total thickness (thickness 2) is (thickness 2) / (thickness 1) = 1/4 to 3/1, physical properties such as shielding properties can be easily adjusted, and sufficient mechanical properties can be obtained. The layer structure in the case of forming a plurality of layers of thin film may be considered as two types of two layers, (B)/(A), or (A)/(B) in which the polyimide layer (B) is disposed on the outer layer of the white layer (A). Two kinds of three layers such as / (A), or two types of five layers such as (B) / (A) / (B) / (AV (B), etc., wherein it is preferable to arrange a polyamine layer in the outer layer. Two types of three layers (B)/(A)/(B) are used because the thickness control is simpler than that of the multilayer film, and the balance between mechanical properties and the like is good. 12 321749 201037023 When there are multiple layers of film, By using the polyamide layer (B) as an outer layer, it is possible to prevent the titanium oxide from oozing out on the surface of the film, and it is possible to make the surface smooth. Thereby, the polyamide resin does not lose its original printability and halftone characteristics. When the film of the plurality of layers is present, the content of the titanium oxide of the white layer (A) is preferably from 10 to 60% by mass, preferably from 20 to 50% by mass. When the content of the titanium oxide is less than 10% by mass, When a plurality of layers of the film are formed, it is difficult to make the content of the titanium oxide 0 to be 5% by mass or more, and it is not easy to obtain a sufficient degree of shielding. On the other hand, when it exceeds 60% by mass, the multilayered layer is formed. When the film is stretched, the cracking frequency is increased, and the productivity is liable to be lowered. When the film is a plurality of layers, the titanium oxide content of the plurality of layers is preferably 40% by mass or less, more preferably 5 to 40% by mass. When the content of the titanium is less than 5% by mass, it is difficult to obtain a sufficient degree of shielding. On the other hand, when the content exceeds 40% by mass, the mechanical properties are deteriorated, and the fracture frequency is increased when the elongation is increased, and the productivity is liable to lower. When a plurality of layers of the film are formed, the polyamidamine layer (B) may be blended with an aromatic polyamide resin for the purpose of improving the hand tearability of the film, etc. The aromatic polyamide resin is only in the form of fat. When the polyglycolamine is blended, the island structure is formed, and the aromatic polyamine resin is used as the island component, and is not particularly limited, and it is possible to use α, ω-fat from xylylenediamine and carbon number 6 to 12. The polyamine structural unit composed of the dicarboxylic acid contains 70 mol% or more of a resin or the like in the molecular chain. Specifically, for example, poly(m-xylylene) m-xylylenediamine, polyheptanylene benzene Guanamine, polyfluorene m-xylylenediamine, poly Homodioxime, polyfluorene terephthalene and other homopolymers, 13 13321749 201037023 diterpene benzodiazepine / hexamethylene terephthalamide copolymer, p-dioxime Dimethylamine/glyoxime-p-xylylenediamine copolymer, anthraquinone-m-xylylenediamine/nonyl-p-xylylenediamine copolymer, indanediamine/indenylhydrazine A copolymer such as a guanamine copolymer, but it is preferably hexamethylene polym-xylylenediamine from the viewpoint of excellent basic properties such as strength and industrially easy to obtain. In the multilayer film, in the polyamide layer ( B) When the aromatic polyamide resin is blended, the aromatic polyamide resin content of the polyamide layer (B) is suitably in the range of 5 to 30% by mass. When the content of the aromatic polyamide resin is less than 5% by mass, the linear cut property is insufficiently found. When the content exceeds 30 mass%/◦, the strength characteristics of the film are deteriorated. The multiple layers of film have a puncture strength of 7. 5N or more is better, and more preferably it is 8. 5N or more. The puncture strength is less than 7. At 5N, when it is used for packaging purposes, because of insufficient puncture resistance, snacks, especially in snacks such as potato chips that are easy to have a firm and sharp angle, may have pinholes when filled by a bag making machine or a packaging machine. Produced. In order to make the puncture strength 7. When 5 N or more, it is necessary to adjust the content of titanium oxide, the titanium oxide layer, and the thickness structure not including the titanium oxide layer. The masking film of the present invention can be produced by the following method or the like. For example, a polyamine resin to which titanium oxide is added is heated and melted in an extruder and extruded into a film shape from a T die, and is cast on a rotating cooling bucket by a known air knife casting method, an electrostatic casting method, or the like. After cooling and hardening, an unstretched film is produced, and the unstretched film is subjected to an elongation treatment to be produced. The masking film of the present invention preferably has a stretched film in order to maintain sufficient strength or puncture strength. The film before stretching was oriented as in the post 14 321749 201037023 . The elongation in the step will decrease, so the thin non-oriented state before stretching is better. It is produced by processing a plurality of layers of film, two, and the like. The temple can also apply the extension ratio of the *extending film, which is better. In the case of vertical and horizontal biaxial stretching, it is more than 5 times L when the (4) is stretched, and the area ratio is usually 3 times. In this range, it can be 1x better. Better still. 5 ^ (4) Extension processing step _ / mechanical properties of the film. Ο 'Special film' is in the tenter of the extension process at 150 to 220. . ^ "The towel field is stolen from 0 to 10%, preferably in the direction of 2 to the money u. The 6/° dry circumference is applied in the longitudinal direction and/or horizontally to reduce the heat of the shielding. The temperature and time are optimized, and the thermal relaxation treatment is performed at a temperature lower than the maximum temperature of the heat-fixing treatment. The L-extension method of the film is not particularly limited, but the method of simultaneous double-hanction extension 0 is When applying the simultaneous biaxial stretching method, the film can be combined with mechanical properties, optical properties, thermal dimensional stability, and pinhole porosity, etc. Other reasons for the biocompatible and simultaneous biaxial stretching method are as follows. In the sequential biaxial stretching method in which the transverse stretching is performed after the longitudinal stretching, the elongation of the polyamide resin in the lateral stretching is lowered due to the directional crystallization of the film in the longitudinal extension, resulting in a high concentration of titanium oxide. The rupture frequency of the film tends to be high. The axial enthalpy of the poly ik private resin film and the biaxially oriented polyester resin 4 film are inferior in dimensional stability. Therefore, generally as a packaging bag, 15 321 749 201037023 The curling phenomenon occurs when it is used. The automatic filling device can not properly grasp the bag and open the bag opening, which may cause leakage of food and other contents. This phenomenon is changed to the horizontally extended manufacturing after the longitudinal extension. The shaft stretching method is very prominent. Therefore, since the curling phenomenon becomes larger along the width direction of the film, the package becomes larger at the end of the film and the half-folded portion near the center portion. The difference in shrinkage ratio occurs because the surface size of the bag is different from the size of the back surface, and curling occurs. In order to suppress the curling phenomenon, it is desirable to use a so-called bowing film which can produce a film having uniform physical properties in the width direction while being double-coated. The shaft stretching method is preferably carried out in a film of a single layer or a plurality of layers thus obtained by performing a surface treatment such as corona discharge treatment. The above film can be suitably used as a material for constituting a packaging material. The sealing layer (Z) is disposed on the film and then heat sealed to form a bag or as a disk (t Ray) The cover material used for packaging, etc. The shape of the bag can be listed, for example, a three-sided sealed bag, a four-sided sealed bag, a pillow bag, a stand-up bag, a rocket type package, etc. As a packaging material using a film, for example, it can be used for: Products, fruits, juices, beverages, wine, conditioning foods, aquatic products, frozen foods, meat products, stews, rice cakes, liquid soups, seasonings, other foods, etc., liquid detergents, cosmetics, cosmetics A filled packaging material such as a finished product. Such a film is composed of a film having high puncture strength and not using aluminum foil, and thus can exhibit an effect in a high-temperature sterilized food prepared by a microwave oven. The shielding layered body of the present invention will be described. 16 321749 201037023 The masking & layering body of this month is at least a material consisting of three layers of a layer of a resin layer (1) / a layer of a binder resin (7) / a layer of dense layer (1). In such a laminate, the amine resin layer (7) of each of the layers (1), (γ), and (7) is usually composed of the above-mentioned single layer or a plurality of layers of the mask film. A lubricant which can be blended in the layer of the polyamine tree (7). 2 == When the layer contains oxidized or a plurality of layers and the outer layer is provided with a layer of titanium oxide, the titanium oxide is exuded to the surface layer of the polyamide resin layer (7) even if no lubricant is added. Also (4) has the role of Run (four). Therefore, not (four) Lion Plus Runlong. But adding is not harmful. Further, in the case of a plurality of layers, when a polyimide layer containing no titanium oxide is provided on the outer layer, it is preferred to add the above-mentioned lubricant to the layer. In the case where the polyamine resin layer constituting the shielding layered body of the present invention contains oxidized crystal as a masking material, the content thereof must be in the range of 5 to 40% by mass in the polyamic acid amine resin layer (7), and 15 to 3〇% by mass is preferred. When the content of titanium oxide is less than 5% by mass, the shielding degree of the shielding layered body is less than 〇〇. 3. In this case, the sufficient light-shielding property to be described later is not obtained, and as a result, the contents are likely to undergo oxidative degradation over time when the food is packaged. On the other hand, when it exceeds 4 mass%, when the polyamide resin is extended, the cracking frequency becomes high, resulting in a decrease in productivity. The film constituting the polyamide resin layer (?) can be produced by the same method as the above-mentioned mask film. In this case, the method of stretching the polyimide film is not particularly limited, and it is preferable to use the simultaneous biaxial stretching method as described above. The upper limit of the titanium content which can be sequentially biaxially stretched is governed by the layer thickness or the stretching ratio. In general, the single layer film is about 321749 201037023 30 mass %, and the plurality of layers film is about 35 mass %. Therefore, in the present invention, it is preferable to carry out the biaxial stretching method while performing the biaxial stretching of the titanium oxide content. In the polyacrylamide resin layer (7), in order to improve the adhesion to the two layers constituting the laminate, that is, the barrier resin layer 〇〇 and the sealant layer (7), it is easy to apply the film treatment on one or both sides. good. For this treatment, the rain often uses two components such as amine vinegar resin, amine vinegar / urea resin to 7. A film of about 0/zm. The utility model has the box-like laminated body towel of the present invention and blocks the dragon layer (not particularly limited. For example, a film of the metal oxide (_) can be used; on the surface of the substrate film = Zhongqi B A film of a barrier resin such as a resin film (4) film, which is a gas-based resin film, or a polyether phthalic acid (Nyl〇nMXD6) or an ethylene glycol copolymer (10)H) Film) and the like. The barrier resin layer (1) may also form a gas barrier coating film layer on the opposite side of the layer of the disk sealant layer in the polyamine resin layer (7). The resin which forms the gas barrier coating layer may, for example, be pVDC, polyvinyl alcohol (PVA), EVOH, %i〇nMXD6, or a resin which exhibits barrier properties such as a modified body. However, there is no particular limitation. The material constituting the barrier resin layer (X) is preferably a film (vapor deposited film) in which a metal oxide is vapor-deposited from the viewpoint of blocking oxygen resistance and blocking water vapority. a substrate film used in the barrier resin layer (X) to be used by polyisene resin, polyamine resin, polyethylene terephthalate resin (ΡΕγ), poly 321749 18 201037023 naphthalene dicarboxylate A film formed of a diester resin or the like is preferable, and a polyester film such as polyethylene terephthalate resin or a polyolefin film such as polyethylene or polypropylene is preferable from the viewpoint of cost and heat resistance. The base film may be either an extensible film, a uniaxially stretched film or a biaxially stretched film, but is preferably a biaxially stretched film from the viewpoint of dimensional stability and mechanical properties. As the vapor deposited layer of the vapor deposited film, an oxide such as aluminum bismuth, zinc or magnesium may be used. Among them, from the oxygen barrier properties and water vapor barrier properties and to the zero surface, the use of oxidation is better. The metal oxide may be either the above alone, or may be a mixture of plural components, or may be a part of the metal component remaining. In the case where the vaporized layer is a metal oxide, since the metal oxide is a complete oxide, it is preferable that the vapor-deposited layer is completely transparent. However, when a complete oxide is usually formed, the probability of forming an excessively oxidized portion is high, and the portion is high. The gas barrier properties are deteriorated, and as a whole, it is difficult to obtain high barrier properties. Therefore, it may be an incomplete oxide film in which some metal components remain. The light transmittance of the vapor-deposited film is preferably 70% or more, preferably 80 ° / 〇 or more, more preferably 85% or more. When the light transmittance of the vapor-deposited film is less than 70%, a relatively large amount of metal component remains in the vapor-deposited layer, and in particular, when it is used as a vapor deposition material, sparks are likely to occur when a microwave oven is used. In the shielding laminate of the present invention, in order to impart necessary oxygen barrier properties, the oxygen permeability of the barrier resin layer (X) is preferably 0 to 100 ml/(m2day·MPa·MPa), preferably 0 to 50 inl. / (m2 · day · MPa), more preferably 0 to 20 ml / (m2 · day · MPa). In the shielding layered body of the present invention, in order to impart the necessary water vapor resistance, the water vapor permeability of the barrier resin layer (X) is preferably 〇1 〇〇g / (m2 _ day). 'It is preferably 0 to 50g / (m2. Day), more preferably ο to 2〇g/(m2· day). For example, a commercially available vapor-deposited film which can be used as the barrier resin layer (X), for example, VM~PET 1011HG-CR (base film··PET, vapor-deposited layer··oxidation) manufactured by Toray Film Processing Co., Ltd., Tohcel HP-BR (base film: PET 'steamed layer: Oxide) manufactured by Mitsubishi Corporation, Techbarrier T (base film: PET, vapor-deposited layer: yttria) manufactured by Mitsubishi Plastics Co., Ltd., ECOSYAR manufactured by Toyobo Co., Ltd. VE100 (base film: PET, steaming layer: ceramics), M0S-TR (base film: pet, steamed key layer: yttrium oxide system) manufactured by Oike Industrial Co., Ltd., and the like. The commercially available coated film which can be used as the barrier resin layer (X) may, for example, be an Emblem DC DCR-15 (base film, nylon 6' coating layer: PVDC) manufactured by Nedica Co., Ltd. Einblet DC KPT-15 made by Dijia Co., Ltd. (substrate film: PET, coating layer: PVDC), Sevix Y0P-15C substrate film made by Nedica Co., Ltd.: nylon 6, coating layer: PVA system + layer The bismuth citrate), Emblem NV-15 (base film, nylon 6, coating layer: polyol polymer + poly- oxo acid polymer) manufactured by Nedica. As a commercially available laminated film which can be used as the barrier resin layer (X), for example, Emblon M Ml00-15 (base film: plural layer MXD 6 series) manufactured by Nedika Co., Ltd., manufactured by Nedica Co., Ltd. EmblonEE301~i5 (base film: multiple layers EV0H series). In the shielding layered body of the present invention, as the resin constituting the sealant layer (Z) of 20 321749 201037023, a low-density polyethylene, a medium-density polyethylene, a high-density polyethylene, a linear polyethylene can be used. Propylene, polyethylene/polypropylene copolymer, ethylene-vinyl acetate copolymer, ionomer (Ionomer) resin, ethylene-acrylic acid/methacrylic acid copolymer, ethylene-acrylic acid/methacrylic acid ester copolymer, poly Vinyl acetate vinegar and other resins. These may be used singly or in the form of copolymerization or melt-mixing with other resins or components, or acid modification. It is also possible to use a plurality of layers of the aforementioned resin component. Particularly preferred are polyhydrazine resins such as polyethylene, polypropylene, and polyethylene/polypropylene copolymers having high heat-sealing strength or high strength of the material itself. The method of forming the sealant layer (Z) may be, for example, a method in which a film or a sheet made of the above-mentioned sealant resin is laminated to a layer of a polyamide resin layer (γ) via an adhesive, and a sealant resin is melt-squeezed and extruded. a method of masking lamination on a layer of aramid resin (Y), a co-extrusion method of simultaneously laminating a layer of a polyimide resin layer (Y) and a sealant layer, and coating on a layer of polyamine resin (Y) The film machine coats a method for forming a resin for forming a sealant layer, and the like. In the case where a film or sheet is formed of a sealant resin, the film or sheet may be in an unextended state or may be in an extended state of low magnification, but it is preferably in an unextended state in practical use. The method for forming the sealant resin film or sheet may be, for example, a tenter method in which a film is heated, melted, and pressed from a press machine, and then cooled and hardened by a cooling roll or the like, or by a tenter method using a cooling roll or the like. After extrusion by a circular molding machine, the cooling method is cooled by water cooling or air cooling. The thickness of the escape layer and the sealant layer (Z) is not particularly limited, and it is more preferably from 40 to 70 #!! with 20 to 100 # m as 隹'. 21 321749 201037023 The shielding of the shielding laminate of the present invention must be 〇. 3 or more, preferably at 0. 4 or more, more preferably 〇·5 or more. When the degree of shielding is less than 〇3, the light-shielding property and the shielding property are insufficient. When the laminated body is packaged, the contents containing oil and fat are easily oxidized and deteriorated, and the contents may be visible because the packaging material is transparent. And thus not good. In order to make the concealer of the laminate become paralyzed. In the range of 3 or more, the content of the masking material such as titanium oxide is adjusted in the polyamine resin layer (Υ) used in the laminate, and the thickness of the polyamide resin layer (Υ) is adjusted. In the case where the masking layered body of the present invention is a white-based masking material such as titanium oxide, the whiteness is preferably from 60 to 100%. It is preferably from 65 to 1%, more preferably from 70 to 100%, and particularly preferably from 8 to 丨〇〇%. When the whiteness is less than 60%, the whiteness is insufficient, and it is fearful that the commercial value of the packaging material is lowered. At the same time, the whiteness of the laminate was measured by the aforementioned method. The whiteness of the laminate can be adjusted by the thickness of the polyimide resin layer and the titanium oxide content. The oxygen permeability of the shielding layered body of the present invention must be 1 〇〇ml/(m2 · day · MPa) or less, and preferably 7 〇mi/(m2 · day · Mpa) or less, at 3 〇ml/(m2 · day · MPa) is more preferable. When the oxygen permeability is higher than 100 ml/(m · day · MPa), the gas barrier property of k after the bag forming process is insufficient, and the content is easily oxidized and deteriorated. The water vapor permeability of the shielding layered body of the present invention is preferably required to be 1 〇〇 g / (ro · day) or less, and the water vapor permeability is greater than 1 〇〇 g / (m 2 · •, the water loss cannot be Neglect, the content is dry and the value of the commodity is reduced. Therefore, at 50g / (m2. The following is preferable to be 321749 22 201037023 20g/(m2 · day) or less. As the pinhole resistance of the shielding layered body of the present invention, the number of pinholes generated in the 5,000 repeated bending fatigue test at 20 ° C is preferably 20 or less. More preferably, it is less than 10. When the number of pinholes is more than 20, when the laminated body is used as a packaging material, holes may be formed in the laminated body when the product or the like is transported. The masking laminate of the present invention can be suitably used as a packaging material. 0 For example, the sealant layer (Z) is heat-sealed, and it can be used as a bag-like body or a package of a lid-like package or the like. The form of the bag may be, for example, a three-sided sealed bag, a four-sided sealed bag, a pillow bag, a stand-up bag, a rocket type package, and the like. The packaging material of the shielding laminate of the present invention can be used to fill packages such as fruits, juices, beverage water, wine, prepared foods, aquatic products, frozen foods, meat products, stews, rice cakes, soups, seasonings, and the like. Food and beverages; liquid detergents; cosmetics; finished products and other contents. In particular, it is suitable for packaging of products containing oils and fats that are susceptible to oxidative degradation, and can be used under the conditions of exposure to sunlight or fluorescent light during display in a store. (Embodiment) Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the Examples. 1. Measurement method The measurement of the following items (1) to (6) was carried out under the conditions of 23 ° C and 50% RH for a sample which was allowed to stand in an environment of 23 ° C and 50% RH for 2 hours or more. 23 321749 201037023 » (1) Thickness of each layer The thickness of each layer was measured by observing the film profile by a scanning electron microscope (SEM). (2) Particle size of inorganic particles The laser diffraction scattering particle size measuring machine SALD-2000 manufactured by Shimadzu Corporation was used for measurement. (3) Whiteness The color spectrum L* is obtained by using a spectrophotometer SE-6000 (manufactured by Sakamoto Denshoku Industries Co., Ltd.). (4) Coverage to take advantage of Markbeth <Only the optical density meter TR932 was used and the light concentration (〇.D.) measured by a penetrating nozzle having a diameter of 3 mm was used as the shielding degree. (5) Puncture strength The film is attached to a ring of 4〇min diameter without loosening. 'Using a tip angle of 60 degrees and a tip bending radius of 〇. 丨之 sapphire needle, 50 imn/min. The speed is punctured into the portion of the film at the center of the circle formed by the ring, and the force at the time of the needle penetration is converted into a film thickness of 1 mm as the puncture strength. (6) The elongation of the shielding film is evaluated as the "good" elongation when the number of occurrences of cracking is less than two times in the middle of the production of the film (10) and (10) by stretching the polyacrylamide resin layer, and the elongation is two or more times. Evaluation as extensibility "bad. (7) Tensile strength <"° 321749 24 201037023 The DSS-500 plotter manufactured by Shimadzu Corporation was measured according to ASTM D882 and evaluated by the average of the MD direction and the TD direction. (8) Tensile strength The DSS-500 plotter manufactured by Shimadzu Corporation was used, and it was measured by ASTM D882 and averaged in the MD direction and the TD direction. (9) Oxygen permeability The oxygen permeability tester (OX-TRAN2/20) made by Mocon (乇>) was used to measure oxygen permeability at a temperature of 20 ° C and a relative humidity of 65%. Ml/(m2 · day · MPa)]. (10) Water Vapor Transmission According to the method described in JIS K-7129 'Measurement of water vapor permeability by PERMATRAN-W1 manufactured by Mocon Corporation at temperature 4 (TC, humidity 90% RH) [g/(m2 · day)]. (11) Pinhole resistance The sheet-like laminate sample of MD300mmxTD200mm size is drawn and held into a cylindrical shape with a diameter of 89mm (3.5 inches) so as to be along the length of the cylinder. The initial holding interval of the direction is 178min (7 inches), so that the grip interval at the time of maximum bending is 25mm (l inch), and the Gruber test machine (the child is only less than one) - made by Rigaku Corporation In the case of 2 (rcx65% RH environment, the bending was performed once, and then the number of pinholes was counted and evaluated. (12) The elongation of the masking laminate was made during the period of making the polyimide layer 1 million per square m 4 film. 'The case where the number of times of splitting will be less than 2 times is that the ping is estimated to be an extension. The case where the number of times is better than the average is evaluated as the extension of the "not true" 321749 25 201037023 2. The raw materials are in the following examples and comparative examples. The raw materials used are as follows: (1) Nylon 6 resin (Ny6) A1030BRF manufactured by Nedica Co., Ltd., relative viscosity 3. 0 (2) Polyhexamethylene Diamine (NXD6) Mitsubishi Gas Chemical Co., Ltd. MX nylon 6〇〇7, relative viscosity 2.6 (3) 鈇 masterbatch in 40 parts by mass of nylon 6 resin, dry blending 60 parts by mass of ruby-type average particle size 〇. 4/m m of titanium oxide (a) (manufactured by Titanium Industries, KRONOS yttrium oxide 1074). The blend was melt-kneaded and extruded into a 30 mm cylindrical twin-screw extruder at a set temperature of 250X: Straight line, after cooling, hardening, cutting, to obtain the grain shape of the titanium masterbatch (a). In 40 parts of nylon 6 resin, dry blending parts of ruby 3L average grain open space. 35 // Titanium oxide (m) of m (manufactured by Titanium Industry Co., Ltd., Ki^NOS titanium oxide KR_3 (8). This compound is kneaded by a 3 Gmm cylinder biaxial (four) machine (4) with a set temperature, _ into a shape, and cold-broken' A titanium masterbatch (5) in the form of a pellet is obtained. Fuji Silysia Corporation, cerium oxide microparticles (SyiysiaSlOP: at this temperature, 1 mixed hemp particle size U core), maintained at 100 ° C, face-mixing - noodle to 26 ^ should The system becomes a uniform sentence. Then it takes another hour to release m to maintain the pressure at L5MPa for 1 hour, 'release [force to become normal pressure for At the time point when the polymerization is completed, the reaction product is poured into a linear shape, and after cooling and hardening, it is cut to obtain particles made of polyamide resin. Secondly, The granules were refined in 95 c of hot water for 8 hours to remove unreacted monomers and the like, followed by addition = drying. The relative viscosity of the oxygen-cut masterbatch to be supplied was such that the content of the silica was 6% by mass. (Example 1) 〇掺 blended with nylon 6 resin (_ with titanium masterbatch (4), as shown in Table m to make oxygen

之圓—"V參配比率成為5質量％ ’供應到溫度設成26〇ΐ 之囫同早輛擠壓機使熔融’從T 成^之冷卻㈣接觸，厚請/之未； =侍未延伸薄片輯在調節成机之溫嫩度18心進行縱向3 進一牛、隹倍之延伸’在斷進行5秒鐘之敎處理，雙Γ在橫方向5%之#他處理，冷卻後得到厚度18 餘鱼中’適t變更鈦母料⑷之思合比率，龙時雙表：未延。之後，藉由同「白色薄㈣含量、厚度之 =?率為3倍、橫心;=，：， ;度疋目的薄膜厚度之10倍。 I伸缚片 (比較例1) 將，_與鈦判⑷彳—⑷之摻配比 27 201037023 · 率成為3質量％。其餘藉由與實施例1同樣之配方，得到厚度180//m之未延伸薄片。之後，與實施例1同樣，藉由同時雙軸延伸法，得到厚度18/im之雙軸延伸白色薄膜。將此稱為「白色薄膜6」。 (參考例1) 除了摻配成鈦母料（a)之摻配比率成為45質量％之外，其餘藉由與實施例1同樣之配方，得到厚度180 μ m之未延伸薄片。將此未延伸薄片藉由與實施例1同樣之配方藉由同時雙軸延伸，得到厚度18/zm之雙轴延伸聚醯胺樹脂膜，然而，切斷頻率高，操作性顯著不良。在實施例1至5、比較例1、參考例1使用之樹脂組成與所得薄膜之特性表示在表1。 28 321749 201037023 [表l]The circle-"V-matching ratio becomes 5% by mass. 'Supply to the temperature set to 26〇ΐ. The same as the early extruder to melt the 'from T to ^ (the) contact, thick please / no; The unstretched sheet is adjusted to the machine's warmth and tenderness, 18 hearts are longitudinally 3 in one ox, and the 隹 times are extended. After 5 seconds of breaking, the double Γ is processed in the horizontal direction by 5%. After cooling, it is obtained. In the thickness of more than 18 fish, the ratio of the titanium masterbatch (4) is changed, and the dragon watch is not extended. After that, by the same "white thin (four) content, thickness = ? rate of 3 times, the center of gravity; =, :, ? degree of film thickness of 10 times. I stretched piece (Comparative Example 1) will, _ and titanium It is judged that the blending ratio of (4) 彳 - (4) is 27 201037023, and the ratio is 3% by mass. The same formulation as in Example 1 is used to obtain an unstretched sheet having a thickness of 180 / / m. Thereafter, as in the case of Example 1, At the same time, the biaxial stretching method was carried out to obtain a biaxially stretched white film having a thickness of 18/im. This was called "white film 6". (Reference Example 1) An unstretched sheet having a thickness of 180 μm was obtained by the same formulation as in Example 1 except that the blending ratio of the titanium master batch (a) was changed to 45% by mass. This unstretched sheet was obtained by simultaneous biaxial stretching by the same formulation as in Example 1 to obtain a biaxially stretched polyamide resin film having a thickness of 18/zm. However, the cutting frequency was high and the workability was remarkably poor. The properties of the resins used in Examples 1 to 5, Comparative Example 1, and Reference Example 1 and the properties of the obtained film are shown in Table 1. 28 321749 201037023 [Table l]

廷伸性 a & & !& & 砬砬凼 ΰ8 iv «ί * - CnJ σ> CD m CD CD to s 'β； Ο) in 史！ t- s \r> σ> Ο) GO s 8 ο 眭彼張強 MPa τ— ?ί CD σ> Ύ— s s s CM s s in 卜· 00 5 CO «ΰ承 E UJ s s σΐ 5§ s 赛黹拿晅琏歡厚度 lim CO o 00 ♦— 齋次 -6 «Ν ΙΟ ΙΟ ΙΟ c\} o § ΓΟ jn 晚輙 Q 联 k ♦— ♦— 4— ♦— * jJ si 齋a? m 茬 in 00 ΙΟ g s Ο) tn 1C m 客 % 2 酱瑤 CSJ 荽 CO « 璀 LO « CD 瑤卜 « 嫌ί 波敌戴 m 戴戴 <fi3 «3 <s3 <fiD <e3 <e) <β3 ·© -0 •Φ i CM CO m 丧诔 « ik ik 201037023 由實施例1至5、比較例卜 β 1至5是得到具備優良機械物性:：如：逃。敝性之白色薄膜。白色度、遮比較例1雖得到優良機械物性 ⑷的摻配量過少，所W色薄膜之遮以^加之氧化鈦度不到0. 3，得；}； $丨奋八 “、又不足，結果遮蔽 Μ载分之錢師遮蔽性。 >歹1 1雖可以得到充分之添加之氧化敘⑷的含量過多，性，但由於㈣，薄膜切斷頻率高’操作计性低’在延伸步際使用者。、·.者不良’是不能供應實 (實施例6) 在尼龍6樹脂中，如矣請質量％之方式摻配氧化石夕母^以=匕^含量成為 :_者相同結構的第1_機，在;二方面，將尼龍6樹脂與鈇母料（a) 配比率成為〗〇質量％之太4 定氧化鈦（a)的摻者相同結構的第2擠 ^投入與在實施例】中所使用機在26〇C熔融擠壓。將在第工 ‘機分舰融之2種樹脂在Μ模中重疊，以源自機之不含氧化鈦的聚醯胺樹脂當作Α層，以源自 A/R/^機之含有氧化欽⑷的白色薄膜當作6層，將Extensibility a &&!&& 砬砬凼 ΰ 8 iv «ί * - CnJ σ> CD m CD CD to s 'β; Ο) in history! - r r GO GO GO GO GO GO GO GO MPa MPa MPa MPa MPa MPa MPa U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U琏厚度 thickness lim CO o 00 ♦ — 斋次-6 «Ν ΙΟ ΙΟ ΙΟ c\} o § ΓΟ jn Late 輙 Q k ♦ — ♦ — 4 — ♦ — * jJ si 斋 a? m 茬in 00 ΙΟ gs Ο) tn 1C m 客 % 2 酱瑶 CSJ 荽CO « 璀LO « CD 瑶卜 « ί 波波戴戴戴戴 fi fi fi (fi3 «3 < ·© -0 •Φ i CM CO m Funeral « ik ik 201037023 From Examples 1 to 5, Comparative Examples β 1 to 5 are obtained with excellent mechanical properties: such as: escape. A white film that is sturdy. In the case of the whiteness and the comparative example 1, the blending amount of the excellent mechanical properties (4) was too small, and the thickness of the W-colored film was less than 0.3, and the amount of the titanium oxide was less than 0.3. As a result, the money is shielded from the Μ Μ 。。。 & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & The user is not able to supply the product. (Example 6) In the nylon 6 resin, if the mass % is mixed, the oxidized stone is mixed with the 母 ^ ^ content to become: _ the same structure The first 1 machine, in the second aspect, the ratio of the nylon 6 resin to the base material (a) is 〇〇 % 4 4 定定定定定定氧化钛氧化钛氧化钛氧化钛氧化钛In the embodiment, the machine used is melt-extruded at 26 ° C. The two kinds of resins melted in the first division of the machine are overlapped in the mold, and the titanium oxide-free polyamine resin is used as the machine. As a layer of ruthenium, a white film containing oxidized chin (4) derived from A/R/^ machine is used as 6 layers.

面溫度T壓模擠壓出來。將其密著在表 ^ 7 Ρ輥同上，得到變成 Α/Β/Λ =40/100/40 /2 ID 之厚度180 i 節成听之溫片。賴得未延伸Μ浸潰在調日内2 /刀鐘，之後在同時雙軸延伸機於延 321749 30 201037023 . 伸溫度180°C下進行縱向3倍、橫向3.3 .進行5秒鐘之熟處理，進一步進行在橫二 .理，冷卻後得到如心之「白_9」=他白處薄膜9」之層結構是Α/β/Α=4/〗0/4/^。 (實施例7至9) 在實施例6中，變更從第】及第層1層各個樹脂組成的比率、各層厚度^機_出的八實施例6同樣操作’得到雙轴延C :其在實施例9 h層並未摻配氧切。稍。/、疋，將如此所狀雙㈣伸至12」。同時，與實施例6同樣，延色相10 為3倍、橫向延伸倍率為3 3倍，未=向延伸倍率部是作成目的薄膜厚度之1〇倍。 /片之厚度，全 (參考例2) _與實_6同樣之配方’得到變成〇 A/B/A=2G/14G/2G#m 之厚度 18G/Zm 之未未延伸薄片與實施例6同樣藉由同時雙轴延伸，^將此之厚度、m之雙軸延伸白= 而，由於三層結構之薄片全體中氧化鈦之含有率古然斷頻率高，操作性顯著不良。 n ’故切 “詳細的實施例6至9、參考例2之樹脂組成薄膜之特性整理在表2。久所得The surface temperature T is extruded. Keep it close to the top of the table, and get the thickness of 180 i into Α/Β/Λ =40/100/40 /2 ID. Lai is not extended and immersed in the day of the 2 / knife clock, then at the same time the double-axis extension machine is extended 321749 30 201037023. The extension temperature is 180 ° C, the longitudinal direction is 3 times, the lateral direction is 3.3. After 5 seconds of ripening, Further, in the case of Heng Er., after cooling, the layer structure of "white_9" = his white film 9" is Α/β/Α=4/〗 0/4/^. (Examples 7 to 9) In the sixth embodiment, the ratio of the composition of each resin in the first layer and the first layer was changed, and the thickness of each layer was the same as in the eighth embodiment. Example 9 The h layer was not doped with oxygen cut. a little. /, 疋, will stretch the double (four) to 12". At the same time, in the same manner as in the sixth embodiment, the color extending phase 10 was 3 times and the lateral stretching ratio was 33 times, and the non-direction extending ratio portion was made 1 time times the thickness of the intended film. /thickness of the sheet, all (Reference Example 2) _ the same formulation as the real _6 - obtained a non-unstretched sheet having a thickness of 18 G/Zm of 〇A/B/A=2G/14G/2G#m and Example 6 By the simultaneous biaxial stretching, the thickness and the biaxial stretching of m are white =, and since the content of titanium oxide in the entire three-layer structure is high, the operability is remarkably poor. n ′′ cutting “Detailed Examples 6 to 9 and Resin Composition of Reference Example 2 The characteristics of the film are summarized in Table 2.

32H 31 201037023 [表2]32H 31 201037023 [Table 2]

簿《特性迪 § S r+^ •cax. 扭 if 穿剌 i強度 N 2 2 CM CO 抗張 ^伸度 % 8 8 8 抗張強度 MPa GO a Γ7 δ CM σ> CO 1»堪靶对· in CD cq σ> 白色度 % S CD CO CD 05 GO ο 薄联结搆廷佧方法 φ 晅 ·— ♦— I 氡化鈦含有董 β量X in CO w 〇總厚度 Aim 00 «Β» ♦— 各層厚度 ptm 4/10/4 6.5/5/6.5 3/12/3 2/14/2 結構 A/B/A ♦— 4— 一 οα 价SR 〇 i? ir> in g m iA 種》軋化鈦 (a) - *— 原料樹脂添加率 1 »量X S in s in c〇原料 ♦—· 4— < 氡化矽母敕名* 1 1 > 原料#1廂 1 1 .. 添加率質量劣 99.92 一 ·— 8 _ 原料一白色辨膜白色薄膜 9 白色薄膜 10 白色薄膜 11 白色薄膜 12 白色辨祺 13 實施例 6 貧施例 7 實掩例 8 贫施例 9 ♦ N 32 321749 201037023 實施例6至9之積層膜，與實施例〗至5之單層白色薄膜相比時，有充分之機械物性，尤其穿刺強度優異。參考例2雖可以得到有充分之遮蔽性/遮光性，但如上述由於氧化鈦的含量過多，不僅比實施例6至9之機械物性下降，在延伸步财，薄膜⑽解也高，操作性不良，因此，是不能供應實際使用者。 (製造例1) Ο &配錢6 _與料料⑷，如表3所示使氧化欽 ⑷，摻配比率成為7質量％，供應到溫度設定在職之圓筒單軸擠麼機内，從Τ愿模擠麗出，與溫度設定成2rc =冷卻輕筒接觸’得到厚度斷m之未延伸薄片。將所得延伸薄片浸潰在調整成5{rc之溫水槽内2分鐘後，夢同時雙轴延伸機於延仲溫度職下進行縱向3倍、择错向由卢廿倍之延# ’在200t進行5秒鐘之熱處理，進一步進行〇方向5%之㈣處理’冷卻後得到厚度18"m之雙轴延〇伸聚酿胺薄膜，將此稱為「聚酿胺薄膜L。 (製造例2至4、6至8、1〇至12) 其餘盘1中’適當變更欽母料之種類 '混合比率，軸延伸:得==樣操作，得到未延伸薄片，藉由同時雙厚度之「= 所示之有各種氧化鈦之種類、含量，製造例/同樣胺涛膜2至4、6至8、1G至。同時，與倍率為心向延伸倍率為3倍、橫向延伸度之10倍。（伸缚片之厚度全部是作成目的薄膜厚 321749 33 2U1U37U23 (製造例5) 以使氧化敎（鈦母料⑷。其餘L之摻配比率成4 20質f %之方式掺配 '餘與製造例1 延伸薄月。將所得之未延伸薄片，：到厚度斷m之未 t：，進行延伸倍率在縱方向延伸溫度60 * ΰ 之延伸，甘伸到3.5倍。之後，在溫度二，在横方向逐次延進一步於溫度如。c之狀態下直接=5秒鐘之熱處理’ 後，於80t冷卻捲取，得到订在橫方向5%之鬆弛薄膜’將此稱為「聚醯胺薄膜；。^之雙輪延伸聚醯胺 (製造例9) 」將尼龍6樹脂、_樹脂樹脂之摻配比率成為1〇質量％二母料（a)，摻配成MXD6 30質量％。其餘與製造例^同铲鈦（a)之摻配比率成為延伸聚醯胺薄犋 &知到厚度18am之雙軸 (製造例13)、 ‘、、、聚酿胺薄膜9」。將尼龍與鈦母料⑷摻率成為30質量％。其餘成氧化鈦（啦摻配比請，之未延伸薄片。之德=5同樣配方，得到厚延伸法得到厚产18//m> 灸/、製造例5同樣，藉由逐次 I伸Μ叫度18//m之雙轴延伸聚延伸步驟中薄膜切斷頻衫mu㈣膜。然而’在例13所得之聚酿胺薄膜稱為「聚 (製造例P) 」將93質量份之低密度聚乙烯樹脂（住友化學公司製 S—e_)wf量份之氧化欽⑷，供給至溫度 321749 34 201037023 . 設定在180°C之圓筒單軸擠壓機，從T壓模擠壓出，與溫度設定成30°C之冷卻輥筒接觸，得到厚度20/im之聚乙烯薄膜。將此稱為「聚醯胺薄膜P」。關於製造例1至13、製造例P之薄膜，將使用之樹脂組成與所得之薄膜特性表示在表3中。Book "Characteristics Di § S r+^ • cax. Twist if 穿剌 i strength N 2 2 CM CO tensile elongation x 8 8 8 tensile strength MPa GO a Γ7 δ CM σ> CO 1» CD cq σ> Whiteness% S CD CO CD 05 GO ο Thin-link structure Tingyi method φ 晅·— ♦— I Tungsten titanium contains Dong β amount X in CO w 〇 Total thickness Aim 00 «Β» ♦—Layer thickness Ptm 4/10/4 6.5/5/6.5 3/12/3 2/14/2 Structure A/B/A ♦—4—one οα price SR 〇i? ir> in gm iA species” rolled titanium (a ) - * - Raw material resin addition rate 1 » Quantity XS in s in c〇 Raw material ♦—· 4— < 氡化矽母敕名* 1 1 > Raw material #1箱1 1 .. Adding rate quality inferior 99.92 ·— 8 _ raw material-white discriminating film white film 9 white film 10 white film 11 white film 12 white identification 13 Example 6 lean example 7 real mask 8 lean example 9 ♦ N 32 321749 201037023 Examples 6 to 9 When the laminated film is compared with the single-layer white film of Examples 7-14 to 5, it has sufficient mechanical properties, and particularly excellent puncture strength. In Reference Example 2, although sufficient shielding property and light blocking property were obtained, the content of titanium oxide was too large as described above, and the mechanical properties of Examples 6 to 9 were not deteriorated, and the film (10) was also high in elongation and operability. Bad, therefore, it is impossible to supply actual users. (Manufacturing Example 1) Ο & dispensed money 6 _ with material (4), as shown in Table 3, the oxidation ratio (4), the blending ratio was 7% by mass, and was supplied to the cylinder of the uniaxial extrusion machine where the temperature was set. I hope that the mold will be squeezed out, and the temperature is set to 2rc = contact with the cooling light cylinder to obtain an unstretched sheet of thickness m. The resulting extended sheet was immersed in a warm water tank adjusted to 5{rc for 2 minutes, and the dream simultaneous biaxial stretching machine was longitudinally 3 times in the longitudinal direction of the temperature, and the wrong direction was extended by Lu Wei times. The heat treatment was carried out for 5 seconds, and further, the 5% (4) treatment in the 〇 direction was carried out. After cooling, a biaxially stretched reinforced amine film having a thickness of 18 Å was obtained, and this was referred to as "polyamide film L. (Production Example 2) To 4, 6 to 8, 1〇 to 12) In the remaining tray 1, 'properly change the type of the masterbatch' mix ratio, the shaft extension: get == sample operation, obtain the unstretched sheet, by the simultaneous double thickness of "= The types and contents of various kinds of titanium oxides are shown, and the production examples/the same amine membranes are 2 to 4, 6 to 8, and 1 Gg. At the same time, the magnification is 3 times the core extension ratio and 10 times the lateral elongation. (The thickness of the stretched sheet is all made to the target film thickness 321749 33 2U1U37U23 (manufacturing example 5) to blend the yttrium oxide (titanium masterbatch (4). The blend ratio of the remaining L is 420 mass f %) Example 1 Extending the thin moon. The resulting unstretched sheet: to the thickness of the broken m is not t:, the stretching ratio is in the vertical The extension temperature of 60 * ΰ is extended to 3.5 times. After that, at temperature two, it is successively extended in the transverse direction at a temperature of, for example, a direct heat treatment of 5 seconds, and then coiled at 80 tons. A loose film of 5% in the transverse direction is obtained. This is called "polyamide film; two-wheel extended polyamine (manufacturing example 9)". The blending ratio of nylon 6 resin and resin resin is 1 〇% by mass of the two masterbatch (a), blended into MXD6 30% by mass. The other blending ratio with the manufacturing example ^ shovel titanium (a) becomes the extended polyamide thinner & Production Example 13), ',, and polyamine film 9'. The blending ratio of nylon and titanium masterbatch (4) was 30% by mass. The balance was made into titanium oxide (the ratio of the blending ratio was not extended). The same formula, the thick extension method is obtained to obtain a thick yield of 18//m> moxibustion/, and the manufacturing example 5 is the same, and the film is cut by the film in the biaxial stretching and stretching step of the yoke degree of 18//m. However, the polyamine film obtained in Example 13 is referred to as "poly (manufacturing example P)" 93 parts by mass of low-density polyethylene resin ( S-e_)wf oxidizer (4) made by Friends Chemical Co., Ltd., supplied to temperature 321749 34 201037023. Cylinder single-axis extruder set at 180 °C, extruded from T die, set to 30 temperature The cooling roll of °C was contacted to obtain a polyethylene film having a thickness of 20/im. This was called "polyamide film P." For the films of Production Examples 1 to 13 and Production Example P, the resin composition and the obtained resin were obtained. The film properties are shown in Table 3.

35 321749 201037023 [表3]35 321749 201037023 [Table 3]

薄膜特性延伸性迪 !& m & IS 1良好| & m 迪丨良好1 & 硇 K- 1 1抗張伸度 % 〇 ΙΟ 〇> Oi GO CO GO <〇 σ> in σ> s S CM 00 CO 1 8 csi 1 抗張強度 MPa g CNJ C0 σ> s τ— CVJ 00 σ> σ> § CM σ> in o S CM g C0 1 S 1- 遮蔽度 LC CO ο GO CD Ο 对 ο 00 卜卜· 〇- S 1 白色度 % CO C0 00 CD 00 CS) 〇 % in CD ΓΟ σ> CO CO LO 〇0 Γ0 in ΙΟ CO LO 〇> 1 m CO 薄膜結構延伸方法密晅 ♦— ♦— 逐次叵 4— — ♦— 逐次 _1 1 厚度 Um 00 ♦— CM ΙΟ CVi CO — m CM ο ΙΟ CSI 00 s 氡化鈦 | 1- 添加率質量％ in in CS) 00 CO o R ♦— 4- CO ΙΟ 8 卜 j 種類 3 i— i 1 4— g 3 4— ♦—· ♦— 原料樹脂资ae S s in CSJ CO s g o 4— § 〇 Ο) in LO 〇 CO σ> 原料 % Z 4— ♦— 4— 4— MXD6 2 低密度聚乙烯雙軸延伸聚醢胺薄膜聚醢胺薄膜1 聚逋胺薄膜2 聚醯胺薄膜3 聚釀胺薄膜4 聚釀胺薄膜5 聚醢胺薄膜6 聚醢胺薄膜7 聚醮胺薄膜8 聚酿胺薄膜9 聚醢胺薄膜10 聚醢胺薄膜11 ............i 聚醯胺薄膜12 聚随胺薄膜13 1 製造例1 | I製造例2 I 1製造例3 1 1製造例4 1 1製造例5 1 1製造例6 1 1製造例7 1 1製造例8 I 製造例9 |製造例ίο I I製造例丨1 I 1製造例12 I I製造例13 I 製造例P 36 321749 201037023 Ο 由表3之結果可知’關於聚醯胺樹脂層之延伸方法，與逐次延伸法相比，可以確認同時延伸法之方法延伸性較優良。詳細地說，在同時延伸法中，如製造例U及12，氧化鈦（a)之含有率即使高到45質量％也可以有良好之延伸。相對於此，在逐次延伸法中，氧化鈦（a)之含有率為 20質量％的製造例5之情形，雖然可以與同時延伸法相同程度地延伸’但在其含有率為30質量％的製造例a之产形，則無法製造薄膜。 @ (實施例10) 對作為聚醯胺樹脂層（Y)之聚醯胺薄膜1的單面實施電暈放電處理’在該電暈處理面上，塗佈接著劑（三井化學聚胺酯公司製 TAKELACA-525/TAKENATEA-52 二液型 f 將經塗佈之薄膜利用80°C之熱風乾燥機乾燥1〇秒鐘，使’ 接著劑塗佈量成為4g/m2。將該接著劑塗佈面與作為阻隔樹脂層（X)之阻隔薄膜（a)(東麗薄膜加工公司製透明蒸^ G薄膜VM-PET1011HG-CR厚度I2#m、蒸鍍膜成分：氧化銘）之蒸鍍處理面，藉由夾輥貼合（夾持條件：8〇t)，得到聚醯胺薄膜1與阻隔薄膜（a)之積層薄膜。進一步對該積層薄膜之聚醯胺面貫施電暈放電處理，在該電暈處理面塗佈接著劑，將作為密封劑層（Z)之密封劑薄膜（a)(Cpp薄膜：東協羅公司（東七口社）製無延伸聚丙烯薄膜RXC_21厚度 50/zm)之電暈處理面重疊，藉由夾輥貼合（夾持條件：δ〇 t)，在40°C環境下老化72小時。藉此，得到由阻隔樹月旨層（X)/聚醯胺樹知層（Y)/密封劑層（Z)之3層所構成的積 32】749 37 201037023 層體。 (實施例11至18、比較例2、參考例3、4) 作為聚醯胺樹脂層者，使用在表4記載之聚醯胺薄膜 2至9、10至12來代替聚醯胺薄膜1。其餘與實施例10 相同處理，而得到積層體。 (實施例19) 作為阻隔樹脂層（X)者，係使用阻隔薄膜（b)(東協羅公司製透明蒸鍍薄膜HP-BR 厚度12//m，蒸鍍膜成分：氧化銘）。其餘與實施例10相同處理，而得到積層體。 (實施例20) 作為阻隔樹脂層（X)者，係使用阻隔薄膜（c)(由尼帝佳公司製Emblet DC KPT-15基材薄膜：PE1T，塗佈層：聚偏二氯乙烯PVDC ;厚度15/zm)。其餘與實施例10相同處理，而得到積層體。 (實施例21) 作為阻隔樹脂層（X)者，係使用阻隔薄膜（d)(由尼帝佳公司製Emb 1 em N V-15，具有有機阻隔塗佈層厚度15#m 之薄膜）。 (實施例22) 作為密封劑層（Z)者，係使用密封劑薄膜（b)(CPP薄膜；東協羅公司製無延伸聚丙烯薄膜RXC-21厚度 80//m)。其餘與實施例10相同處理，而得到積層體。 (實施例23) 作為密封劑層（Z)者，係使用密封劑薄膜（c)(線狀低 38 321749 201037023 密度聚乙烯；多摩玻麗公司株）製聚乙烯薄膜 UB-3，厚度50//m)。其餘與實施例10相同處理，而得到積層體。 (比較例3) 作為聚醯胺樹脂層（Y)者是使用聚醯胺薄膜8。阻隔樹脂層（X)係使用未實施蒸鍍之PET薄膜（由尼帝佳公司製Film Properties Extensibility Di & m & IS 1 Good | & m Di Di Hao 1 & K K-1 1 Tensile Strength % 〇ΙΟ 〇> Oi GO CO GO <〇σ> in σ&gt s S CM 00 CO 1 8 csi 1 Tensile strength MPa g CNJ C0 σ> s τ — CVJ 00 σ> σ gt § CM σ> in o S CM g C0 1 S 1- Shielding degree LC CO ο GO CD Ο ο 00 卜卜 S - S 1 whiteness % CO C0 00 CD 00 CS) 〇% in CD ΓΟ σ> CO CO LO 〇0 Γ0 in ΙΟ CO LO 〇> 1 m CO film structure extension method 晅 ♦ — ♦ — Successive 叵 4 — ♦ — Successive _1 1 Thickness Um 00 ♦—CM ΙΟ CVi CO — m CM ο ΙΟ CSI 00 s Titanium Titanium | 1- Addition Mass % in in CS) 00 CO o R ♦ — 4- CO ΙΟ 8 卜 j Type 3 i— i 1 4— g 3 4— ♦—· ♦— Raw material resin ae S s in CSJ CO sgo 4—§ 〇Ο) in LO 〇CO σ> Raw material % Z 4-— ♦— 4— 4— MXD6 2 Low Density Polyethylene Biaxially Extended Polyamide Film Polyamide Film 1 Polyamide Film 2 Polyamide Film 3 Polyurethane Film 4 Poly Amine film 5 Polyamide film 6 Polyamide film 7 Polyamide film 8 Polyamide film 9 Polyamide film 10 Polyamide film 11 ............i Polyamide film 12 Polyamine film 13 1 Production Example 1 | I Production Example 2 I 1 Production Example 3 1 1 Production Example 4 1 1 Production Example 5 1 1 Production Example 6 1 1 Production Example 7 1 1 Production Example 8 I Production Example 9 | Production Example ί 2 II Production Example I 1 I Production Example 12 II Production Example 13 I Production Example P 36 321749 201037023 Ο From the results of Table 3, it is understood that the method for extending the polyamide resin layer can be confirmed as compared with the sequential stretching method. At the same time, the method of the extension method is more excellent in extensibility. In detail, in the simultaneous stretching method, as in Production Examples U and 12, the content of the titanium oxide (a) can be favorably extended even if it is as high as 45% by mass. On the other hand, in the case of the production example 5 in which the content of the titanium oxide (a) is 20% by mass in the sequential stretching method, it can be extended to the same extent as the simultaneous stretching method, but the content thereof is 30% by mass. In the production form of the production example a, the film could not be produced. @ (Example 10) Corona discharge treatment was performed on one side of the polyimide film 1 as the polyamide resin layer (Y). On the corona-treated surface, an adhesive was applied (TAKELACA, manufactured by Mitsui Chemicals, Polyurethane Co., Ltd.) -525/TAKENATEA-52 Two-component type f The coated film was dried by a hot air dryer at 80 ° C for 1 , second, so that the amount of the subsequent coating was 4 g / m 2 . As a barrier film (a) of the barrier resin layer (X) (a transparent vapor deposition film of Toray Film Processing Co., Ltd., VM-PET1011HG-CR thickness I2#m, vapor deposition film component: oxidation), by the vapor deposition treatment surface The nip roller is bonded (clamping condition: 8 〇t) to obtain a laminated film of the polyimide film 1 and the barrier film (a). Further, the polyacrylamide surface of the laminated film is subjected to corona discharge treatment, and the electricity is applied thereto. The halo-treated surface is coated with an adhesive, and the sealant film (a) as a sealant layer (Z) (Cpp film: non-stretched polypropylene film RXC_21 thickness 50/zm manufactured by Toray Industries, Inc.) The corona-treated surfaces were overlapped and aged by a nip roll (clamping condition: δ〇t), and aged at 40 ° C for 72 hours. A product layer consisting of three layers of a barrier layer (X)/polyamine tree layer (Y)/sealant layer (Z) was obtained. 749 37 201037023 Layers. (Examples 11 to 18, comparison Example 2, Reference Example 3, 4) As the polyimide resin layer, the polyamide film 2 to 9, 10 to 12 described in Table 4 was used instead of the polyamide film 1. The rest was treated in the same manner as in Example 10, (Example 19) As the barrier resin layer (X), a barrier film (b) (a transparent vapor-deposited film manufactured by Toray Industries, Inc. HP-BR thickness 12/m, vapor deposition film component: oxidation) was used. In the same manner as in Example 10, a laminate was obtained. (Example 20) As the barrier resin layer (X), a barrier film (c) (Emblet DC KPT-15 based by Nedica) was used. Material film: PE1T, coating layer: polyvinylidene chloride PVDC; thickness 15/zm), and the same treatment as in Example 10 was carried out to obtain a laminate. (Example 21) As a barrier resin layer (X), A barrier film (d) (Emb 1 em N V-15 manufactured by Neddy Co., Ltd., film having an organic barrier coating layer thickness of 15 #m) was used. (Example 22) For the sealant layer (Z), a sealant film (b) (CPP film; non-stretch polypropylene film RXC-21 thickness: 80/m) manufactured by Tosoh Co., Ltd. was used, and the rest was treated in the same manner as in Example 10 to obtain (Example 23) As the sealant layer (Z), a polyethylene film UB-3 made of a sealant film (c) (linear low 38 321749 201037023 density polyethylene; Tamaori company) was used. Thickness 50//m). The rest was treated in the same manner as in Example 10 to obtain a laminate. (Comparative Example 3) As the polyamine resin layer (Y), a polyimide film 8 was used. Barrier resin layer (X) is a PET film that has not been vapor-deposited (made by Nedica)

EmbletPET-12，厚度12yni)，取代阻隔薄膜（a)。其餘與 ^實施例10相同處理，而得到積層體。〇 (比較例4) 聚醯胺樹脂層（Y)係使用製造例P所得之含有氧化鈦之聚乙烯薄膜。其餘與實施例10相同處理，而得到積層體。整理實施例10至23、比較例2至4、參考例3、4之積層體特性在表4中。〇 39 321749 201037023 積層體耐針孔性锢 <〇卜〇 <D 〇 σ> to m CO (〇 r? Csi ¢5 卜水蒸氣穿透度 g/(m*-day) GO 00 00 CO CO 00 GO CO u> ΙΟ 0D GO CO GO 00 C0 00 氡氣穿透度 mlAnr^-day· MPa) tn in in tr> ID tA ο V™* in CM s 卜 LA LO ΙΓ5 in § m 遶蔽度 S LO g S s 5 g t^m 5 S 5 5 s 〇- 卜 σ> 〇· 〇' 白色度 % z δ s σ> CO 00 CM CD CO GO CM GO LO 〇 ΙΟ CD 1〇 CO S CM CO CM 〇> (Π CD 密封劑層 (Z) 密封#!薄膜(a) 十密銬劑薄联⑹ I密封劑薄膜(C) 密封劑薄膜(a) ♦— 4— 阻热樹磨層 (X) 阻隔薄膜（a) «I— 4» 阻隔薄貘（b) 1阻蹣薄膜(c) 阻鵑辦联(<0 阻隔薄膜（a) » 4— 4— PET薄膜阻隔薄膜（a) 聚醢按樹脂層 (Y) 1聚醢肤薄膜1| 聚醮肢薄膜2 聚醢胺薄膜3 聚醯胺薄膜4 1聚醢胺薄胰5 I 聚醞胲薄膜6 聚醢胺薄祺7 聚醢胺缚獏8 1聚醯胺薄膜9 | 聚醮胺缚膜1 4— 聚醯胺薄膜彳0 聚醢胺薄膜Η 聚醢胺薄膜12 聚酿肢薄膜8 聚乙烯薄膜 |實施例ίο I |實施例| 1實施例丨2 I |實施例丨3 I I實施例彳4 I L實施例15」 1實施例16 | 1實施例π 1 I實施W 18 I 1實施例彳9 I 1實施例20 I |jr施例211 |實施例22 | 丨賞施例23 1 1比較例2 1 1參考W3 I 1參考例4 I 比較例3 比較例4 由實施例10至23、比較例2至4、參考例3、4，得知如下。 40 321749 201037023 在貝％例10至23可得遮蔽性、氧氣阻隔性、水蒗5 阻隔性，異之積層體。此全部因為沒有使用氧化料氧化銘蒸鑛樹脂㈣，所以具備微波爐適用性、又可以葬由金屬探測機檢查異物。曰曰比較例2係在聚酿胺樹脂層⑺中，由於氧化鈦之摻 :己量少’故遮蔽性不足，結果積層體之遮蔽度不足〇 3: 得不到充分之遮光性或遮蔽性。Emblet PET-12, thickness 12yni), replaces the barrier film (a). The rest was treated in the same manner as in Example 10 to obtain a laminate.比较 (Comparative Example 4) The polyamine resin layer (Y) was a polyethylene film containing titanium oxide obtained in Production Example P. The rest was treated in the same manner as in Example 10 to obtain a laminate. The laminate properties of Examples 10 to 23, Comparative Examples 2 to 4, and Reference Examples 3 and 4 were summarized in Table 4. 〇39 321749 201037023 Multilayer pinhole resistance 锢<〇卜〇<D 〇σ> to m CO (〇r? Csi ¢5 卜 water vapor permeability g/(m*-day) GO 00 00 CO CO 00 GO CO u> ΙΟ 0D GO CO GO 00 C0 00 Helium penetration mlAnr^-day· MPa) tn in in tr> ID tA ο VTM* in CM s 卜 LA LO ΙΓ5 in § m Winding S LO g S s 5 gt^m 5 S 5 5 s 〇- 卜σ> 〇· 〇' whiteness % z δ s σ> CO 00 CM CD CO GO CM GO LO 〇ΙΟ CD 1〇CO S CM CO CM 〇> (Π CD sealant layer (Z) seal #! film (a) tens of tantalum thinner (6) I sealant film (C) sealant film (a) ♦ - 4 - heat-resistant tree grinding layer (X ) Barrier film (a) «I—4» Barrier film (b) 1 Barrier film (c) Barrier film (<0 barrier film (a) » 4—4—PET film barrier film (a)醢Pressing resin layer (Y) 1 Polythene film 1| Poly leg film 2 Polyamide film 3 Polyamide film 4 1 Polyamide Thin pancreatic 5 I Poly film 6 Polyamide thin 祺 7 醢Amine 貘8 1 Polyamide film 9 | Polyamide film 1 4 - Polyamide film 彳0 Polyamide film 醢 Polyamide film 12 Poly sorbent film 8 Polyethylene film | Examples ίο I | Examples | 1 Example I 2 I | Example II 3 II Example 彳 4 IL Example 15 ” 1 implementation Example 16 | 1 Example π 1 I Implementation W 18 I 1 Example 彳 9 I 1 Example 20 I |jr Example 211 | Example 22 | Appreciation Example 23 1 1 Comparative Example 2 1 1 Reference W3 I 1 Reference Example 4 I Comparative Example 3 Comparative Example 4 From Examples 10 to 23, Comparative Examples 2 to 4, and Reference Examples 3 and 4, the following were found. 40 321749 201037023 In the case of Examples 10 to 23, shielding, oxygen barrier can be obtained. Sexuality, leeches 5 barrier properties, different laminates. All of this is because there is no oxidized oxide oxidized mineral resin (4), so it has the applicability of the microwave oven, and can be buried by a metal detector to check foreign matter. 曰曰Comparative example 2 is in In the polyacrylamide resin layer (7), since the amount of titanium oxide added is small, the shielding property is insufficient, and as a result, the shielding degree of the laminated body is less than 〇3: sufficient light shielding property or shielding property is not obtained.

參考例3、4係在聚醯胺樹脂層（γ)中，由於氧化鈦之掺配量過多’故積層Κ針孔性下降，積層體之針孔生個數超過2G個。使用有此程度之該積層體作為包誓材情形’運送商品等之際，在積層體可能會產生孔洞，因此參考例3、4是不能供給實用者。比車乂例3因為使用沒有實施蒸鑛或阻隔性之塗佈的膜，故氣體阻隔性不足。 /# 比較例4因為沒有使用聚酿胺樹脂層（γ)作為積層體中間層，故為本發明之範圍以外者。因此，性，但耐針孔性差。付判h蚊 (製造例14) θ在尼龍6樹月旨（Ny6)中，如表5所示以使氧化石夕之含置成為〇· 08質量％之方式掺配料料，投人與在製造例I 使用者相同結構的擠壓機—i内’在26〇。。熔融擠壓。一方面’將尼龍6顏與鈦料⑷，錢⑽鈦之摻配比率換配=質量％之方式，投入與在製造例】使用者相同結構之擠塵機-2内，在26rc熔融擠壓。將分別在_機_卜 321749 41 201037023 擠壓機-2烙融之2種樹脂在壓模機中重疊，將源自擠壓機 -1之不含氧化鈦的聚醯胺樹脂當作A層，將源自播壓機-2 之含氧化銶的聚醯胺樹脂當作B層，將A/B/A之三層結構之薄片從T壓模機壓出。將其密著在表面溫度2〇°c之冷卻輥筒上，得到A/B/A=20/140/20 /zm之厚度180/im的未延伸薄片。將所得未延伸薄片浸潰在調整在50°c之溫水槽中 2分鐘’之後以同時雙轴延伸機於延伸溫度igot下進行縱向3倍、横向3. 3倍之延伸’在2〇〇°c進行5秒鐘之熱處理’進一少進行在橫方向5%之鬆弛處理，冷卻後得到雙軸延伸之厚度18 //m之「聚醯胺薄膜14」。此聚醯胺薄膜14 之層結構是 Α/Β/Α=2/14/2//ιη。 (製造例15至22、24、26至31) 與製造例14相比，將由擠壓機、擠磨機—2擠廢出之A層、b層各別之樹脂組成、複數層薄臈之層結構、各層In Reference Examples 3 and 4, in the polyamide resin layer (γ), since the amount of titanium oxide is too large, the pinhole porosity of the laminate is lowered, and the number of pinholes in the laminate is more than 2G. When the laminate is used as the smuggling material, when a product or the like is transported, a hole may be formed in the laminated body. Therefore, the reference examples 3 and 4 cannot be supplied to a practical person. The gas barrier property is insufficient because the film of the coating which is not subjected to steaming or barrier property is used. /# Comparative Example 4 is not included in the scope of the present invention because the polyamine resin layer (?) is not used as the intermediate layer of the laminate. Therefore, it is sexual, but it is poor in pinhole resistance. In the Ny6, Ny6, as shown in Table 5, the ingredients of the oxidized stone are set to 〇·08% by mass, and the ingredients are mixed. Production Example I The user of the same structure of the extruder - i inside 'at 26 〇. . Melt extrusion. On the one hand, 'the ratio of the blending ratio of nylon 6 and titanium (4) to the weight of titanium (10) is replaced by = mass%, and it is put into the duster-2 of the same structure as the user of the manufacturing example, and melt-extruded at 26rc. . The two kinds of resins which are respectively melted in the machine_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The cerium oxide-containing polyamine resin derived from the weaving press-2 was used as the B layer, and the sheet of the three-layer structure of A/B/A was extruded from the T molding machine. This was adhered to a cooling roll having a surface temperature of 2 ° C to obtain an unstretched sheet having a thickness of 180 / im of A / B / A = 20 / 140 / 20 / zm. The resulting unstretched sheet was immersed in a warm water bath adjusted to 50 ° C for 2 minutes', and then extended by 3 times in the longitudinal direction and 3 times in the transverse direction at the extension temperature igot. c. The heat treatment was carried out for 5 seconds. The relaxation treatment was carried out in a 5% direction in the transverse direction, and after cooling, a "polyamide film 14" having a thickness of 18 // m which was biaxially stretched was obtained. The layer structure of the polyamide film 14 is Α/Β/Α = 2/14/2//ιη. (Manufacturing Examples 15 to 22, 24, 26 to 31) In comparison with Production Example 14, a resin layer of the A layer and the b layer which were extruded by the extruder and the squeeze mill-2 was composed of a plurality of layers of thin resin. Layer structure, layers

之厚度改成如表5所示。其餘藉由進行與製造例14相同之才呆作，得到雙軸延伸聚醯胺薄膜。只是，造例18中，A ，不換配氧化⑦。將所得之雙軸延伸㈣胺薄膝分別物1 聚醯胺薄膜15至22、24、26至31」。同時與製造例\ 同延伸時之縱向延伸倍率是3倍、橫向延伸借率禾未延伸薄片之厚度全部是設定成目衫之传 (製造例23) 处 ^ 投入擠壓機-2之樹脂組成物係以使氧化鉢（a)的摻齡 ^成為40質量％之方式，摻配尼龍6樹脂與妹脅科（a) 其餘藉由與製造例14相同之配方，得刻 321749 42 201037023 A/B/A=30/120/30 /im之厚度180/zm的未延伸薄片。將所得未延伸薄片’於延伸溫度60艺下在縱方向進行延伸倍率 2. 8倍之延伸，其次，在橫方向進行3. 5倍之逐次延伸。之後，在20(TC進行5秒鐘之熱處理，進一步在溫度21〇 °C之狀態下在橫方向進行5%之鬆弛後，在別它冷卻後捲取’藉此’得到成為A/B/A=3/12/3//m之經雙軸延伸之厚度18//m之「聚醯胺薄膜23」。The thickness was changed as shown in Table 5. The rest was carried out in the same manner as in Production Example 14, to obtain a biaxially stretched polyimide film. However, in the case of Example 18, A is not replaced with oxidation 7. The resulting biaxially stretched (tetra)amine thin knees were each separated into a polyamide film 15 to 22, 24, 26 to 31". At the same time, the longitudinal extension ratio is 3 times, the lateral extension ratio, and the thickness of the unstretched sheet are all set to be passed down to the eyepiece (Manufacturing Example 23). The system was blended with a nylon 6 resin in the same manner as in the case where the age of the cerium oxide (a) was 40% by mass, and the rest of the formulation was the same as in the production example 14, and the 321749 42 201037023 A/ Unstretched sheet of thickness 180/zm of B/A = 30/120/30 /im. 5倍的延伸延伸。 The extension of the extension of the film was carried out in the longitudinal direction of the stretching ratio of 2. 8 times the extension, followed by the lateral direction of 3.5 times the sequential extension. Thereafter, at 20 (the TC was heat-treated for 5 seconds, and further 5% relaxation was performed in the horizontal direction at a temperature of 21 ° C, and after it was cooled, the winding was taken 'by this' to obtain A/B/ A = 3/12/3//m "polyamide film 23" having a thickness of 18/m which is biaxially stretched.

❹ (製造例25) B層樹脂組成是製作成尼龍6樹脂/MXD6樹脂/氧化鈦 (a)=50/10/40(質量％)。其餘藉由與製造例14相同之配方’得到A/B/A=30/120/30 /im之厚度l80"m白勺未延伸薄片。使用所得未延伸薄片，藉由與製造例14相同之配方，知到成為A/B/A=3/12/3 e m之經雙轴延伸之厚戶a _ 「聚醯胺薄膜25」。 X 之 (製造例32) B層樹脂組成是製作成尼龍6樹脂/氧化鈦（如㈣ (質量。其餘藉由與製造例丨4相同之配方，得 A/B/A=20/14()/2Mm之厚度⑽_的未延伸=。將所得未延伸溥片藉由與製造例23相同之配方經由延伸，雖欲得到成為峨__2/14/2_之厚度軸延伸聚醯胺㈣，但切_率變高，操作性又而得不到該薄膜。將製造例32欲得到之聚醒胺膜’ 「聚醯胺薄膜32」。寻膜稱為將詳細之製造例U至32的樹脂版成、及所得薄膜之 321749 43 201037023 特性，整理在表5中表示。 [表5] 薄膜特性㈣盎 a 扭 Η- •Ok 位ί 迪 a & m Η-· § s ΰ: 迪 a 迪迪 § & & & S 眹靶+ 这奪$ S N CO in 对 φ 二 s s ΙΑ 8 S S 〇 S 1 抗張強度 MPa 8 CM Ο s s «Μ CO s €SJ s CM s OJ s CM § 〇 5 CM s S ir> (D S esi 1 S CD oq ID s s g r-· lO g 5 00 5 00 5 5 1 白色度 % S s s s s δ s g S S S s Κ Ξ S Μ ! 薄祺結構廷伸方法 « Ιϋ — ♦— ♦— Li*j m 晅 Φ» ·— «— 4— 4mm *— Η 阉氧化鈦含有t 質量X CO η C4 O) ra r- n n 00 卜 TT CO Γ0 S CO 5 对總厚度 ί/τη CO s o 00 ♦— 4— 一 00 C0 各層厚度 2/14/2 *— 4— 6/6/6 | 4/3/4/3/4 4/17/4 1/8/1 3/12/3 4/10/4 1/16/1 I 1 1/7.5/1/7.5/1 1 16/3/16 2/14/2 層結搆 A/B/A «- ·— B/A/B 1 CD A/B/A/B/A j A/B/A < 一一 ·—» 一 ω A/B/A/B/A A/B/A % Α/Β/Α 氡化鈦添加率赁黃X o 8 s ·— *— B S <— § 8 〇 in 5? 〇 S? *— 8 S 種類 3 ♦» V— «>» ♦— 4— 2 3, ·— 一一 4— 原料樹脂添加率 t量X s 〇 s A s s s S 〇 to σ> S 8 s R S 隳 m 1 *— 1— *— 一 ♦— ♦— MXD6 I φ— *— < 氣化矽齋ΛΡ i o 1 ♦— t l *—· » 4-· ·— ·— » 一 » 種類 % Z 一一一嶂· — 一 ·— - — — — 一 — 雙軸廷伸聚飙胺簿膜 I聚醯胺辦祺H 聚醯胺薄旗15 聚醯胺薄康16 聚》胲薄《 17 1聚醣胺薄膜18 |聚釀胺薄膜19 聚醯胺縳旗20 1聚醯胺辦旗21 聚醯胺薄膜22 聚醯胺薄旗23 聚*胺薄膜24 聚醣胺簿膜25 聚醯胺薄琪26 1聚醯胺辦膜27 I |聚鵝胺溥膜28 聚釀胺薄祺29 ! 聚醯胺薄膜30 j I聚鷗胺薄蜞31 I聚醯胺薄膜32 \e> CO 卜 00 σ> s κ 25 S S S a r<J <〇 44 321749 201037023 如表5所示，複數層薄膜中，關於延伸方法，確認與 . 逐次延伸法相比’同時延伸法延伸性較優異。由與表3之 ,結果相對比，確認聚醯胺樹脂層（Y)複數層薄膜比單層者的抗張強度及抗張伸度更優良。 (製造例24) •對聚醯胺薄膜14之單面實施電暈放電處理，在該電暈處理面上’塗佈接著劑（三井化學聚胺醋公司製擺〇 Α 525/ΤΑΚΕΝΑΊΈΑ-52二液型），將經塗佈之薄膜利用8〇 °C之熱風乾燥機乾燥10秒鐘，使接著劑塗佈量成為 _。將該接著劑塗佈面與作為阻隔樹脂層⑴之在實施例1〇使用者相同阻隔薄膜⑷之蒸鍍處理面，藉由夾親貼。（夾持條件.80 C) ’得到聚酿胺薄膜14與阻隔薄膜⑷ ^積層薄膜it纟對該積層薄膜之聚醯胺樹脂面實施電暈放電處⑤纟該電暈處理面上塗佈接著劑，將作為密封一層⑺之與只化例1()相同之密封劑薄膜⑷之電晕處理面重宜，藉由夾輥貼合（夾持條件：8〇。〇，在4〇。〇環境下老化72小時。传到由阻隔樹脂層⑴/聚醯胺樹脂層⑺/ 密封劑層⑺之3層所構成的積層體。 (實施例25至39、比較例5至9、參考例5、6) 作為聚醯胺Μ脂層⑺、阻隔樹脂層⑴、密封劑層⑵ 者仏使用在表6 5己載之薄膜，與實施例相同處理，而得到各別之積層體。整理貫施例24至39、比較例5至9、參考例5、6之積層體物性在表6中。 45 321749 201037023 [表6] * ii η 右單 IF C0 〇 ΙΟ CO CO 卜 u> 〇〇 1» €•5 ο »·» r> LO S (D \r> 私？ 00 C0 C0 00 CO 00 0Q C0 CO CO 00 CD 00 00 00 00 CO CD C0 G0 〇 00 9 «ϋ ^ 相f i κί令. wf Έ ΙΟ u> u> ΙΟ ΙΟ in ir> LO to ir> ir> Γ9 ΙΑ P0 to tr> ii> u> u> 1» 卜 lf> S «ν 帮 2 S § S g IT> S 卜, s CD S S s s Ο- n 5 W. 〇 »· 〇' ο* 〇· «) t s S CO δ w s s σ> 3 s » S 3 s s s s m S S Oi Ο s Ϊ Q * w 褰篥篆 4— ♦— *— ♦— * 在 * 褲 3 戴 9c 3 m 戴 w «Μ 4— ，丨_ 礮 I8 Μ 3 篇欲 £ 4— — ·— S « « £ S « £ 3 m « £ 扭 «» «>*> 赛 m Id 0. |s 濾被雄瀘 1A « 戴濾 CD 戴 m Λ 卜 i 戴 CD n 戴雄濾〇) 蒙饉邃戴 * 鶬欲 te 璀戴餹 H » * 戴濾 S Μ 戴雄餹葛 m 雄瘺裹 «r 隹濾皸雄餹 « 戴雄鱷璀戴雄餹褰戴鱷 Μ 戴饍褰戴 * 在 δ |κ; δ Ic δ 嫌 u 〇 « Ic 1« S 3P 嫌 $· ΪΚ 妹 V? η « s IK tr> τ a a in 在 ♦ K& $ CD 卜 «1 •ΰ 00 5 Si ·£ tn «1 -£ 貫施例24至39是遮蔽性、氧氣阻隔性、水蒸氣阻隔性優良之積層體。因為此等全部沒有使用氧化鋁箔、氧化銘蒸鍍樹脂薄膜，所以具備微波爐適用性、又可以藉由金屬探測機檢查異物。 46 321749 201037023 比較例5、6、7、8係在聚醯胺樹脂層中，由於氧化鈦之摻配量少，故聚醯胺樹脂層之遮蔽度不足，結果積層體之遮蔽度不足0. 3，得不到充分之遮光性或遮蔽性。參考例5、6係在聚酸胺樹脂層中，由於氧化鈦之# 配量過多，故積層體之耐針孔性下降，積層體之針孔產生個數超過20個。此程度之積層體，作為包裝使用之情形，運送商品等之際，在積層體中可能會產生孔洞，因此為不能供給實用者。比較例9因為使用沒有實施蒸鍍或阻隔性塗佈等之薄膜，故氣體阻隔性不足。【圖式簡單說明】無【主要元件符號說明】無 47 32]749制造 (Production Example 25) The B layer resin composition was prepared into a nylon 6 resin/MXD6 resin/titanium oxide (a) = 50/10/40 (% by mass). The remainder was obtained by the same formulation as in Production Example 14 to obtain an unextended sheet having a thickness of A/B/A = 30/120/30 /im. Using the obtained unstretched sheet, by the same formulation as in Production Example 14, it was found that the biaxially stretched thick a_ "polyamide film 25" which became A/B/A = 3/12/3 e m. (Production Example 32) The B layer resin composition was made into nylon 6 resin/titanium oxide (as in (4) (mass. The rest was obtained by the same formulation as in Production Example 4, and A/B/A=20/14() was obtained). /2Mm thickness (10)_ is not extended =. The obtained unstretched ruthenium is extended by the same formulation as in Production Example 23, and although the thickness axis of the 峨__2/14/2_ is extended, the polyamine (4) is obtained. However, the film has a high cleavage rate and the operability is not obtained. The polyimide film "polyamide film 32" to be obtained in Production Example 32 is used. The film formation is referred to as the manufacturing examples U to 32 in detail. The resin plated, and the resulting film of 321749 43 201037023 characteristics, finishing is shown in Table 5. [Table 5] film properties (four) ang a twist - • Ok bit ί di a & m Η - · § s ΰ: di a Didi § &&& S 眹 target + this to win $ SN CO in to φ two ss ΙΑ 8 SS 〇 S 1 tensile strength MPa 8 CM Ο ss «Μ CO s €SJ s CM s OJ s CM § 〇5 CM s S ir> (DS esi 1 S CD oq ID ssg r-· lO g 5 00 5 00 5 5 1 whiteness % S ssss δ sg SSS s Κ Ξ S Μ ! Thin 祺 structure stretching method « Ιϋ— ♦— ♦— Li*jm 晅Φ» ·— «— 4— 4mm *— Η 阉 titanium oxide contains t mass X CO η C4 O) ra r- nn 00 卜 TT CO Γ0 S CO 5 to total thickness ί/ Ηη CO so 00 ♦— 4— 00 C0 thickness of each layer 2/14/2 *— 4— 6/6/6 | 4/3/4/3/4 4/17/4 1/8/1 3/12 /3 4/10/4 1/16/1 I 1 1/7.5/1/7.5/1 1 16/3/16 2/14/2 Layer structure A/B/A «- ·- B/A/B 1 CD A/B/A/B/A j A/B/A < One-to-one» One ω A/B/A/B/AA/B/A % Α/Β/Α Titanium addition rate租黄X o 8 s ·— *— BS <— § 8 〇in 5? 〇S? *— 8 S Type 3 ♦» V— «>» ♦— 4— 2 3, ·—一一四— Raw material resin addition rate t amount X s 〇s A sss S 〇to σ> S 8 s RS 隳m 1 *— 1 — *— ♦ — ♦ — MXD6 I φ— *— < gasification 矽 ΛΡ io 1 ♦— tl *—· » 4-· ·—·—» One» Category% Z 一一嶂· — 一·— — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — H Polyamide thin flag 15 Polyamide thin Kang 16聚胲胲"17 1 Glycine Amine Film 18 | Polyamide Film 19 Polyamide Acetone Flag 20 1 Polyamide Banner 21 Polyamide Film 22 Polyamide Thin Flag 23 Polyamine Film 24 Glycan Amine Film 25 Polyamide Bianqi 26 1 Polyamide film 27 I | Polyergentamine film 28 Polyamide thin film 29 ! Polyamide film 30 j I Polyurethane thin film 31 I Polyamide film 32 \e> CO 00 σ gt s κ 25 SSS a r < J < 〇 44 321749 201037023 As shown in Table 5, in the multi-layer film, regarding the extension method, it is confirmed that the simultaneous extension method is compared with the sequential extension method. More excellent. From the results of Table 3, it was confirmed that the multilayer film of the polyamide resin layer (Y) was more excellent in tensile strength and tensile strength than the single layer. (Production Example 24) • Corona discharge treatment was performed on one side of the polyimide film 14, and an adhesive was applied on the corona treatment surface (Mitsui Chemical Polyamine Vinegar Co., Ltd. 525/ΤΑΚΕΝΑΊΈΑ-52 Liquid type), the coated film was dried by a hot air dryer at 8 ° C for 10 seconds to make the amount of the adhesive applied to _. This adhesive-coated surface was adhered to the vapor-deposited surface of the barrier film (4) which is the same as the user of the barrier resin layer (1). (Clamping condition: 80 C) 'The obtained polyamine film 14 and the barrier film (4) are laminated film. The surface of the polyimide film of the laminated film is subjected to a corona discharge. The corona treatment surface of the sealant film (4) which is the same as the sealant film (4) of the seal layer (7) is preferably applied by a nip roll (clamping condition: 8 〇. 〇, at 4 〇. 〇 The mixture was aged for 72 hours in the environment, and passed through a laminate composed of three layers of the barrier resin layer (1) / polyamide resin layer (7) / sealant layer (7). (Examples 25 to 39, Comparative Examples 5 to 9, Reference Example 5 6) As the polyimide film layer (7), the barrier resin layer (1), and the sealant layer (2), the film which has been carried out in Table 65 is used, and the same process as in the Example is carried out to obtain a separate laminate. The physical properties of the laminates of Examples 24 to 39, Comparative Examples 5 to 9, and Reference Examples 5 and 6 are shown in Table 6. 45 321749 201037023 [Table 6] * ii η Right single IF C0 〇ΙΟ CO CO 卜 u> 〇〇 1» €•5 ο »·» r> LO S (D \r> Private? 00 C0 C0 00 CO 00 0Q C0 CO CO 00 CD 00 00 00 00 CO CD C0 G0 〇00 9 «ϋ ^ ΙΟ in ir> LO to ir>ir> Γ9 ΙΑ P0 to tr>ii>u>u> 1» 卜 lf> S «ν 帮 2 S § S g IT> S 卜, s CD SS ss Ο- n 5 W. 〇»· 〇' ο* 〇· «) ts S CO δ wss σ> 3 s » S 3 ssssm SS Oi Ο s Ϊ Q * w 褰篥篆 4— ♦—*— ♦—* In * pants 3 wearing 9c 3 m wearing w «Μ 4— , 丨 _ 礮 I8 Μ 3 pieces for £ 4 — — — S « « £ S « £ 3 m « £ Twist «» «>*> Race m Id 0. |s Filtered by 泸 1A « Wear filter CD wear m Λ 卜 i wear CD n Dai Xiong filter 馑邃馑邃馑邃鶬鶬 te te 璀 » » » » » » » » Filter S Μ Dai Xiong 餹 m m 瘘瘘 « «r 隹皲皲餹戴戴戴戴戴戴戴戴戴戴戴戴戴戴戴戴在在在在在在在在在在在在在在 I I I I I I I I I I I I I I I S 3P $ $· ΪΚ sister V? η « s IK tr> τ aa in ♦ K& $ CD 卜 «1 • ΰ 00 5 Si · £ tn «1 - £ Example 24 to 39 is masking, oxygen Excellent barrier properties and water vapor barrier properties Layer body. Since all of these are not used in the alumina foil or the oxidized vapor-deposited resin film, the microwave oven is suitable for use, and the foreign matter can be inspected by a metal detector. 46 321749 201037023 Comparative Examples 5, 6, 7, and 8 are in the polyimide resin layer. Since the amount of titanium oxide is small, the shielding degree of the polyamide resin layer is insufficient, and as a result, the shielding degree of the laminated body is less than 0. 3, not enough shading or shielding. In Reference Examples 5 and 6, in the polyamic acid resin layer, since the amount of titanium oxide was too large, the pinhole resistance of the laminate decreased, and the number of pinholes in the laminate was more than 20. In this case, when the product is used as a package, when a product or the like is transported, a hole may be formed in the laminated body, and therefore it is not possible to supply a practical person. In Comparative Example 9, since a film which was not subjected to vapor deposition or barrier coating was used, gas barrier properties were insufficient. [Simple description of the diagram] None [Main component symbol description] None 47 32] 749

Claims

201037023 VII. Patent application scope: A kind of shielding film, the shielding degree of the 苴 pile 舛在在 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Material, and the whiteness is 65 to 1_. "5. The masking film of the second item of the application, which contains titanium oxide K and contains 60 to 95% by mass of the polyamide resin. 4. The patent application range is the Gansu > The concealing film of the item of at least one single-layer layer containing titanium oxide, 5% by weight, and containing 40% by mass to 90% by mass of the polyamide resin is composed of a polyamine resin containing no titanium oxide. The layered body of the second layer has a puncture strength of 7 or more. The masking film of any one of items 2 to 4, wherein the main component of the polyamide resin is nylon 6. The shielding film of any of items 2 to 4 of the "Patent Patent Range" is a simultaneous biaxial stretching. 7. & a kind of cover layer, which is a layer containing at least a barrier resin layer (1), a polyimide resin layer (7) composed of a concealing film of the first patent of the patent application scope, and a sealant layer (7) And the shielding degree is 〇. 3 or more, and the oxygen permeability is l〇〇ml/(m2 · day · MPa) or less. 8. The masking laminate according to item 7 of the patent application, wherein the water vapor permeability is 100 g/(m2 · day) or less. 9. The shielding layered body of claim 7 or 8, wherein the number of pinholes generated when the bending fatigue test of repeated 5 times is performed in an environment of 2 〇 ° C x 65% RH is 2 One below. 321749 48 201037023 10. The masking laminate according to claim 7 or 8, wherein the whiteness is 60 to 100%. 11. A packaging material consisting of a masking laminate of claim 7 or 8. ❹ 49 321749 201037023 . φ IV. Designated representative figure: There is no drawing in this case (1) The representative drawing of the case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: This case is not represented by the chemical formula 321749. Patent No. 99101447 ϋ橐.. 汐9年5月1一声日) 201037023 « > Can be listed as: clay, talc, calcium carbonate, zinc carbonate, wollastonite, yttria, alumina, magnesia, calcium citrate, sodium aluminate: sulphur, about; 5 magnesium silicate, glass beads (glassbali〇〇n), carbon oxides, oxidized bismuth oxide, zeolite, hydrotalcite, layered sulphate, double stearin, ethylenediamine, and the like. Among them, the oxidized stone eve is also preferred. The content of the lubricant in the polyamide resin is suitably in the range of 〇·〇1 to 〇.3 mass%.遮蔽 In the masking film of the present invention, a masking material is contained. As a masking material, j cattle can be oxidized, barium sulfate, oxidized, vulcanized, and carbonated. Curved titanium is preferred. The reason is that when the above-mentioned masking material = attacking direction is contained in the (tetra) amine resin, a small amount of the masking material is obtained as a titanium oxide, and the content of the titanium oxide is preferably 5 至 5 qn # θ 40% by mass is particularly preferred from 15 to 30% by mass. When the content of the titanium oxide is less than 5 〇 to 〇.3, the charge as described later is not obtained, and the degree of shielding of the bonded film becomes unsatisfactory. On the other hand, when the temperature exceeds 40 lbs/〇, the productivity is liable to decrease in addition to the decrease in mechanical properties. The frequency of the rupture at the time of the extension The particle type of the titanium oxide contained in the sputum is not limited to any one of the types such as the type of the glutinous ore and the gold red. However, it is preferred to use a brookite redstone type titanium oxide from the two lle) type. From the viewpoint of shielding, it is known that gold is photoactive on titanium oxide, and it is produced on the surface of titanium oxide particles. In detail, ultraviolet rays are irradiated from the base. When this radical enters the polymerization of the substrate, the decomposition of the polymer chain occurs, which becomes the main cause of yellowing of the film. Therefore, it is preferred that the titanium oxide particles are subjected to surface treatment. The surface treatment has inorganic treatment and organic treatment. ... as an inorganic processor, aerobic treatment, oxygen cutting treatment, titanium oxide treatment, oxidation treatment, tin oxide treatment, cerium oxide treatment, zinc oxide treatment, etc., of which oxidation treatment is also preferred. The organic processor may be, for example, a polyol such as pentaerythritol 'trimethylolpropane; an amine such as triethanolamine or trihydroxydecylamine; or a treatment with an oxygen-based treatment such as a decyloxy resin or an alkyl gas oxime. The particle diameter of the titanium oxide is not particularly limited, but is preferably in the range of 〇 ^ to 0.5 / zm, and preferably in the range of from 0.2 to /.4 / /m. When the average particle diameter is less than 0.1 m, the dispersibility in the polyamide resin is poor, and the coarse coagulum is dispersed in the film, and the occurrence of pinholes in the film causes the value thereof to decrease. On the other hand, when the average particle diameter exceeds 0.5 #!!!, when the polyimide resin layer is formed into a film, the frequency of film breakage becomes high, and the productivity tends to sag. The method of blending titanium oxide in the polyamine resin is not particularly limited and may be blended at any point in the production step. For example, a method of adding titanium oxide at the time of polymerization of polyfluorene = day, a high concentration of TiO 2 in a polyamide resin, and a masterbatch for adding it to a polyamide resin, and then adding it to the polyimide resin Master batch), a method of melt-mixing a polystyrene tree and a titanium oxide machine. In the Ming Dynasty, it is better to adjust to the titanium oxide concentration before the film formation by using the master batch method. ^ 321749 10 201037023 The shielding degree of the masking film of the present invention must be 3% or more, preferably 0.4 or more, more preferably 0.5 or more. When the degree of shielding is less than 0.3, the light-shielding property and the shielding property are insufficient, and the content of the fat or the like is deteriorated, the oxidation is deteriorated, and the contents are transparent because they are visible, which is not preferable. In order to adjust the degree of shielding of the film to 0.3 or more, the content of the titanium oxide may be adjusted within the range defined by the present invention, and the thickness of the shielding film may be adjusted. In the present invention, the degree of masking means the optical density (O.D.) measured by an optical densitometer. The larger the value, the higher the shielding. The masking film of the present invention preferably has a whiteness of 65 to 100%. It is preferably from 75 to 100%, particularly preferably from 85 to 100%. When the whiteness is less than 65°/◦, since the whiteness is insufficient, the value of the product may be lowered if the packaging material is required to be innovative. In the present invention, the whiteness is a value obtained by measuring the whiteness of a sample by a spectroscopic colorimeter SE-6000 manufactured by Sakamoto Electric Co., Ltd. according to a reflection method and a test method of JIS Z8729. The whiteness is obtained from the L* value of the L*a*b* value representing the 3 stimulus values of the color. The whiteness of the thin film can be adjusted by the thickness of the film and the amount of titanium oxide as a masking agent. The tensile strength of the masking film of the present invention is preferably 180 MPa or more, preferably 190 to 220 MPa. When the tensile strength is less than 180 MPa, the mechanical strength is insufficient and the puncture strength tends to be deteriorated. The tensile strength of the film is preferably 80% or more from the viewpoint of the tensile strength, and more preferably 90 to 120%. The thickness of the shielding film of the present invention can be appropriately adjusted according to the necessary degree of shielding, or the intended mechanical strength, or the intended whiteness, etc. 11 321 749 201037023 Patent Application No. 99101447. (May 14, 1999) ) Choose. When the film is supplied as a packaging, the thickness thereof is preferably from 10 #m to 30 // m, preferably from 15/zm to 30/zm, from the viewpoint of mechanical strength and ease of handling. When the film thickness is less than 10 #πι, sufficient mechanical strength is not obtained, and the puncture strength tends to be deteriorated. The total thickness at the time of producing the laminate is preferably from 10 Å to 30/zra, more preferably from 15/m to 30 mM, for the same reason, and can be favorably used as a masking film of the present invention. It is easy to form a single layer film. On the other hand, a polyamine-containing resin layer (B) containing no titanium oxide is formed on at least one side of the white layer (A) containing 10 to 60% by mass of the titanium oxide resin and containing 40 to 90% by mass of the polyamide resin. The multi-layer film can provide high shielding properties as compared with a single-layer film, and can also improve mechanical properties, and in particular, can improve puncture strength. The white layer (A) and the polyamide resin layer (B) may also be present in plural. When forming a plurality of layers of film, the thickness of the singular or plural white layer (A) and the singular or plural polyamine resin layer (B), when the total thickness of the (A) layer (thickness 1) and (B) When the ratio of the total thickness (thickness 2) of the layer is (thickness 2) / (thickness 1) = 1/4 to 3/1, physical properties such as shielding properties can be easily adjusted, and sufficient mechanical properties can be obtained. The layer structure in the case of forming a plurality of layers of a film may be considered as two types of two layers of (B)/(A), or (A)/() in which the polyimide layer (B) is disposed on the outer layer of the white layer (A). Two types of three layers, such as B)/(A), or two types of five layers, such as (B)/(A)/(B)/(A)/(B). Among them, two types of three layers of (B) / (A) / (B) of the polyamide resin layer are preferably disposed on the outer layer. The reason for this is that the thickness control is simpler than that of the multilayer film, and the balance of mechanical properties and the like is good. 12 321749 Rev. 201037023 Patent Application No. 99101447 (May 99) 4) When a plurality of layers of film are used, by using the polyimide resin layer (B) as an outer layer, it is possible to prevent titanium oxide from oozing out on the surface of the film, and It may make the surface smooth. Thereby, the polyamide resin can be obtained without losing the printing property and the halftone property originally possessed. In the case of a plurality of layers of film, the content of titanium oxide of the white layer (A) is preferably from 10 to 60% by mass, preferably from 20 to 50% by mass. When the content of the titanium oxide is less than 10% by mass, when a plurality of layers of the film are formed, it is difficult to make the content of the titanium oxide 5 mass% or more, and it is not easy to obtain a sufficient degree of shielding. On the other hand, when the film of the multilayer structure is stretched in an amount of more than 60% by mass, the cracking frequency is increased and the productivity is liable to be lowered. When the film has a plurality of layers, the titanium oxide content of the plurality of layers is preferably 40% by mass or less, more preferably 5 to 40% by mass. When the content of the titanium oxide is less than 5% by mass, it is difficult to obtain a sufficient degree of shielding. On the other hand, when it exceeds 40% by mass, in addition to a decrease in mechanical properties, the cracking frequency becomes high at the time of extension, and productivity is liable to lower. In the case of forming a plurality of layers of the film, the polyamine resin layer (B) may be blended with an aromatic polyamide resin for the purpose of improving the hand tearability of the film or the like. The aromatic polyamine resin may be formed into a sea-island structure when blended with an aliphatic polyamine, and an aromatic polyamine resin may be used as an island component, and is not particularly limited, and benzodiazepine may be used. The polyamine structural unit composed of an α,ω-aliphatic dicarboxylic acid having 6 to 12 carbon atoms contains 70 mol% or more of a resin or the like in the molecular chain. Specifically, for example, polyhexamethylene phthalamide, polyheptaphthalene methylene dimethylamine, polyfluorene m-xylylenediamine, polyfluorene diphenyl phthalamide, polyfluorene均醯醯曱等等 13 13 13 13 13 13 2010 2010 2010 370 370 370 370 370 370 370 370 370 370 370 370 370 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010庚醯苯苯曱 / / / 庚醯醯醯醯醯共聚物共聚物共聚物共聚物共聚物共聚物醯醯醯醯醯醯共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物共聚物A copolymer such as a diterpene terpene amine copolymer is preferred from the viewpoint of excellent basic properties such as strength and industrially easy to obtain, and it is preferably hexamethylene poly(p-xylylenediamine). In the multi-layer film, when the polyamide resin layer (B) is blended with the aromatic polyamide resin, the aromatic polyamide resin content of the polyamide resin layer (B) is in the range of 5 to 30% by mass. To be appropriate. When the content of the aromatic polyamide resin is less than 5% by mass, the linear cut property is insufficient, and when it exceeds 30 mass%/〇, the strength characteristics of the film are deteriorated. The film thickness of the plurality of layers is preferably 7. 5 N or more, more preferably 8.5 N or more. When the puncture strength is less than 7. 5N, when it is used for packaging purposes, because of the lack of puncture, the snacks, especially in snacks such as horse chestnut chips, which are easy to have sharp and sharp corners, are made by bag making machine or packaging. There may be pinholes when the machine is filled. In order to make the puncture strength to be 7. 5 N or more, it is necessary to adjust the content of the titanium oxide, the titanium oxide layer, and the thickness structure not including the titanium oxide layer. The masking film of the present invention can be produced by the following method or the like. For example, a polyamine resin to which titanium oxide is added is heated and melted in an extruder and extruded into a film shape from a T die, and is cast on a rotating cooling bucket by a known air knife casting method, an electrostatic casting method, or the like. After cooling and hardening, an unstretched film is produced, and the unstretched film is subjected to an elongation treatment to be produced. The masking film of the present invention preferably has a stretched film in order to maintain sufficient strength or puncture strength. The film before stretching is oriented, as in the last 14 321749 revision