TWI687308B - Multi-layer structure, packaging materials and products using it, and protective sheets for electronic devices - Google Patents
Multi-layer structure, packaging materials and products using it, and protective sheets for electronic devices Download PDFInfo
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- TWI687308B TWI687308B TW104143614A TW104143614A TWI687308B TW I687308 B TWI687308 B TW I687308B TW 104143614 A TW104143614 A TW 104143614A TW 104143614 A TW104143614 A TW 104143614A TW I687308 B TWI687308 B TW I687308B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/50—Containers, packaging elements or packages, specially adapted for particular articles or materials for living organisms, articles or materials sensitive to changes of environment or atmospheric conditions, e.g. land animals, birds, fish, water plants, non-aquatic plants, flower bulbs, cut flowers or foliage
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Abstract
本發明為有關一種多層結構體,其為含有基材(X),與層合於前述基材(X)之層(Y)的多層結構體,前述層(Y)為,含有含鋁之化合物(A)與聚乙烯醇系樹脂之磷酸酯化物(BP),前述聚乙烯醇系樹脂之磷酸酯化物(BP)之磷酸酯化率RBP為0.15以上。 The present invention relates to a multilayer structure which is a multilayer structure comprising a substrate (X) and a layer (Y) laminated on the aforementioned substrate (X), the aforementioned layer (Y) being a compound containing aluminum (A) Phosphate (BP) with the polyvinyl alcohol resin, the phosphate esterification rate R BP of the phosphate ester (BP) of the polyvinyl alcohol resin is 0.15 or more.
Description
本發明為有關多層結構體、使用其之包裝材料及製品,與電子裝置之保護薄片之發明。 The present invention relates to a multilayer structure, packaging materials and products using the same, and a protective sheet for electronic devices.
使用鋁或氧化鋁作為構成成份之氣體阻隔層形成於塑膠薄膜上之多層結構體,以往即廣為已知者。該些多層結構體,多被作為保護容易受到氧而產生變質之物品(例如,食品)的包裝材料使用。該些氣體阻隔層中之大多數為,使用物理氣相成長法(PVD)、化學氣相成長法(CVD)等乾製程,而形成於塑膠薄膜上者。又,該些多層結構體,亦被使用作為以保護電子裝置之特徵為目的之被要求具有氣體阻隔性及水蒸氣阻隔性之電子裝置的保護薄片之構成構件。 Multi-layer structures formed of a gas barrier layer using aluminum or aluminum oxide as a constituent component on a plastic film are widely known in the past. These multilayer structures are often used as packaging materials for protecting articles (for example, food) that are susceptible to oxygen and deteriorate. Most of these gas barrier layers are formed on the plastic film by using dry processes such as physical vapor growth (PVD) and chemical vapor growth (CVD). In addition, these multilayer structures are also used as constituent members of protective sheets for electronic devices that are required to have gas barrier properties and water vapor barrier properties for the purpose of protecting the characteristics of electronic devices.
例如,鋁蒸鍍薄膜,除具有氣體阻隔性以外,亦具有遮光性,主要為作為乾燥食品之包裝材料使用。 For example, in addition to gas barrier properties, aluminum vapor-deposited films also have light-shielding properties, and are mainly used as packaging materials for dry food.
另一方面,具有透明性之氧化鋁蒸鍍薄膜, 具有可辨識內容物,及可使用金屬探測機進行異物檢査或可使用微波爐進行加熱等特徵。因此,該薄膜,由殺菌袋食品(retort pouch food)包裝開始,而廣泛地被使用作為包裝材料之用途。 On the other hand, a transparent aluminum oxide vapor deposition film, It has the characteristics of recognizable content, and the use of metal detectors for foreign object inspection or the use of microwave ovens for heating. Therefore, this film has been widely used as a packaging material since retort pouch food packaging.
具有含有鋁之氣體阻隔層的多層結構體,例如,具有由氧化鋁粒子與磷化合物之反應產物所構成之透明氣體阻隔層的多層結構體已被專利文獻1所揭示。形成該氣體阻隔層之方法之一,於塑膠薄膜上塗佈含有氧化鋁粒子與磷化合物之塗覆液,其次進行乾燥及熱處理之方法已被專利文獻1所揭示。 A multilayer structure having a gas barrier layer containing aluminum, for example, a multilayer structure having a transparent gas barrier layer composed of a reaction product of alumina particles and a phosphorus compound has been disclosed in Patent Document 1. One method of forming the gas barrier layer is to apply a coating liquid containing aluminum oxide particles and a phosphorus compound on a plastic film. The method of drying and heat treatment is disclosed in Patent Document 1.
但是,以往之具有氣體阻隔層的多層結構體,於初期多具有優良之氣體阻隔性,但因變形、衝撃等受到物理性壓力之際,而於氣體阻隔層產生裂縫或沙孔等缺陷,而會有造成氣體阻隔性降低之情形。 However, the conventional multi-layer structure with a gas barrier layer often has excellent gas barrier properties at the initial stage, but when physical pressure is applied due to deformation, impact, etc., defects such as cracks or sand holes occur in the gas barrier layer, and There may be cases where the gas barrier property is reduced.
因此,已有一種不僅具有優良之氣體阻隔性,且即使受到變形、衝撃等受到物理性壓力之際,氣體阻隔性亦可維持於高效率之多層結構體已被專利文獻2所揭示。 Therefore, there has been disclosed a multi-layered structure that not only has excellent gas barrier properties but also maintains high gas barrier properties at high efficiency even when subjected to physical stress such as deformation and impact.
但是,本發明者們,將專利文獻1及專利文獻2所揭示之多層結構體作為殺菌袋食品之包裝材料使用時,會有殺菌處理後的層間接著力會降低,而會產生無法層合等外觀不良之情形。又,本發明者們將專利文獻1及專利文獻2所揭示之多層結構體使用於電子裝置時,於進行溫濕試驗後則會產生層間剝離之情形。 However, when the present inventors use the multilayer structure disclosed in Patent Document 1 and Patent Document 2 as packaging materials for sterilization bag foods, the interlayer adhesion after sterilization treatment may be reduced, resulting in failure to laminate, etc. The appearance is bad. In addition, when the inventors use the multilayer structure disclosed in Patent Document 1 and Patent Document 2 for electronic devices, delamination may occur after the temperature and humidity test.
因此,目前急需尋求一種即使殺菌處理後,也具有良好特性的氣體阻隔性之多層結構體。及,一種使用於高溫.高濕下亦具有高層間接著力,且,具有高阻隔性之多層結構體的電子裝置。 Therefore, there is an urgent need to find a multi-layer structure having good gas barrier properties even after sterilization treatment. And, one used in high temperature. Under high humidity, it also has an adhesive force between high layers and an electronic device with a multilayer structure with high barrier properties.
[專利文獻1]WO2011/122036號 [Patent Literature 1] WO2011/122036
[專利文獻2]特開2013-208793號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2013-208793
本發明之目的為,提供一種具有優良氣體阻隔性及水蒸氣阻隔性的同時,亦具有優良耐殺菌性之新穎的多層結構體及使用其之包裝材料。 The object of the present invention is to provide a novel multi-layer structure with excellent gas barrier properties and water vapor barrier properties, as well as excellent sterilization resistance and packaging materials using the same.
又,本發明之其他目的為,提供一種使用具有優良氣體阻隔性及水蒸氣阻隔性,且於高溫.高濕下亦具有高層間接著力之新穎的多層結構體的電子裝置之保護薄片。 In addition, the other object of the present invention is to provide a use having excellent gas barrier properties and water vapor barrier properties, and at high temperatures. A protective sheet for electronic devices with a novel multi-layer structure that also has adhesion between high layers under high humidity.
經過深入研究結果,本發明者們,發現含有特定之層的多層結構體即可達成上述之目的,因而完成本發明。 After intensive research, the inventors found that a multilayer structure containing a specific layer can achieve the above-mentioned object, and thus completed the present invention.
本發明為提供一種多層結構體,其為含有基材(X),與層合於前述基材(X)之層(Y)的多層結構體,前述層(Y)為,含有含鋁之化合物(A)與聚乙烯醇系樹脂之磷酸酯化物(BP),前述聚乙烯醇系樹脂之磷酸酯化物(BP)之磷酸酯化率RBP為0.15以上。 The present invention is to provide a multilayer structure which is a multilayer structure containing a substrate (X) and a layer (Y) laminated on the substrate (X), the layer (Y) being a compound containing aluminum (A) Phosphate (BP) with the polyvinyl alcohol resin, the phosphate esterification rate R BP of the phosphate ester (BP) of the polyvinyl alcohol resin is 0.15 or more.
本發明之多層結構體中,前述含鋁之化合物(A),可為含有含鋁之金屬氧化物(Aa)與無機磷化合物(BI)之反應產物(D)之化合物(Ab)。 In the multilayer structure of the present invention, the aluminum-containing compound (A) may be a compound (Ab) containing the reaction product (D) of the aluminum-containing metal oxide (Aa) and the inorganic phosphorus compound (BI).
本發明之多層結構體中,前述聚乙烯醇系樹脂之磷酸酯化物(BP)之磷酸酯化率RBP亦可為0.24以上。 In the multilayer structure of the present invention, the phosphate esterification rate R BP of the phosphate ester compound (BP) of the polyvinyl alcohol-based resin may be 0.24 or more.
本發明之多層結構體中,前述磷酸酯化物(BP)中,下述通式〔III〕所表示之磷酸酯化乙烯醇單位可含有15.0~99.8莫耳%。 In the multilayer structure of the present invention, the phosphated vinyl alcohol unit represented by the following general formula [III] in the phosphate ester (BP) may contain 15.0 to 99.8 mol %.
本發明之多層結構體中,前述基材(X)中,可含有由熱塑性樹脂薄膜及紙所成群所選出之至少1種之層。 In the multilayer structure of the present invention, the substrate (X) may contain at least one layer selected from the group consisting of thermoplastic resin films and paper.
又,本發明為提供一種含有前述任一個多層 結構體之包裝材料。 Moreover, the present invention is to provide a layer containing any of the foregoing Packaging materials for structures.
前述包裝材料可再具有由擠壓塗覆層合所形成之層。 The aforementioned packaging material may further have a layer formed by extrusion coating lamination.
前述包裝材料,可為縱製袋填充密封袋、真空包裝袋、袋(pouch)、層合管狀容器、輸注液袋(bag)、紙容器、長條袋、容器用蓋材,或可為模內標籤容器。 The aforementioned packaging material may be a vertical bag filled and sealed bag, a vacuum packaging bag, a pouch, a laminated tubular container, an infusion solution bag (bag), a paper container, a long bag, a cover material for a container, or may be a mold Inner label container.
此外,本發明為提供一種製品,其為使用前述任一包裝材料作為至少一部份者。 In addition, the present invention is to provide an article using any of the aforementioned packaging materials as at least a part.
前述製品可為,含有內容物、內容物為芯材、製品內部經減壓,且具有真空隔熱體之機能者。 The aforementioned product may be one that contains contents, the contents are core materials, the inside of the product is decompressed, and has the function of a vacuum heat insulator.
又,本發明又提供一種含有前述任一個多層結構體之電子裝置的保護薄片。 Furthermore, the present invention provides a protective sheet for an electronic device containing any one of the aforementioned multilayer structures.
前述電子裝置之保護薄片,可為保護光電變換裝置、資訊顯示裝置,或照明裝置之表面的保護薄片。 The protective sheet of the electronic device may be a protective sheet for protecting the surface of the photoelectric conversion device, the information display device, or the lighting device.
又,本發明為提供一種含有前述任一個保護薄片的電子裝置。 Furthermore, the present invention is to provide an electronic device including any of the aforementioned protective sheets.
依本發明之內容,可製得一種具有優良氣體阻隔性及水蒸氣阻隔性,亦具有優良耐殺菌性之新穎的多層結構體及使用其之包裝材料。即,依本發明之內容,可製得一種不僅具有優良的氣體阻隔性及水蒸氣阻隔性,殺菌處理後亦可維持優良之氣體阻隔性及水蒸氣阻隔性的同時,殺菌處理後也不會產生剝離(delamination)等外觀不良 情形,而具有高度層間接著力(剝離強度)之新穎的多層結構體及使用其之包裝材料。又,依本發明之內容,可得一種使用具有優良氣體阻隔性及水蒸氣阻隔性,於高溫.高濕下亦具有高層間接著力之新穎的多層結構體的電子裝置之保護薄片。即,依本發明之內容,可製得一種不僅具有優良的氣體阻隔性及水蒸氣阻隔性,於溫濕試驗後亦可維持優良氣體阻隔性及水蒸氣阻隔性的同時,溫濕試驗後也不會產生剝離等外觀不良情形,而具有高度層間接著力(剝離強度)之含有新穎的多層結構體之保護薄片的電子裝置。 According to the content of the present invention, a novel multi-layer structure with excellent gas barrier properties and water vapor barrier properties, as well as excellent sterilization resistance and packaging materials using the same can be prepared. That is, according to the content of the present invention, it is possible to obtain an excellent gas barrier property and water vapor barrier property, which can maintain excellent gas barrier property and water vapor barrier property after sterilization, and will not Defective appearance such as delamination In this case, there is a novel multilayer structure with high interlayer adhesion (peel strength) and packaging materials using the same. In addition, according to the content of the present invention, one can obtain an excellent gas barrier property and water vapor barrier property at high temperature. A protective sheet for electronic devices with a novel multi-layer structure that also has adhesion between high layers under high humidity. That is, according to the content of the present invention, it is possible to obtain a product that not only has excellent gas barrier properties and water vapor barrier properties, but also maintains excellent gas barrier properties and water vapor barrier properties after a temperature and humidity test, as well as after a temperature and humidity test An electronic device containing a protective sheet with a novel multi-layer structure having a high interlayer adhesion (peel strength) without causing appearance defects such as peeling.
10‧‧‧縱製袋填充密封袋 10‧‧‧ Vertical bag filled with sealed bag
11‧‧‧多層結構體 11‧‧‧Multi-layer structure
11a‧‧‧端部 11a‧‧‧End
11b‧‧‧本體部 11b‧‧‧Body
11c,411,412,413,414,611‧‧‧周邊部 11c, 411,412,413,414,611
20‧‧‧平袋(flat pouch) 20‧‧‧flat pouch
360‧‧‧容器 360‧‧‧Container
361、362、363‧‧‧多層標籤 361, 362, 363‧‧‧ multilayer labels
361a‧‧‧貫通孔 361a‧‧‧Through hole
370‧‧‧容器本體 370‧‧‧Container body
371‧‧‧凸緣部 371‧‧‧Flange
372‧‧‧本體部 372‧‧‧Body
373‧‧‧底部 373‧‧‧Bottom
371a‧‧‧凸部 371a‧‧‧Convex
40‧‧‧電子裝置 40‧‧‧Electronic device
41‧‧‧電子裝置本體 41‧‧‧Electronic device body
42‧‧‧密封材料 42‧‧‧Sealing material
43‧‧‧保護薄片(多層結構體) 43‧‧‧Protection sheet (multilayer structure)
401‧‧‧輸注液袋(bag) 401‧‧‧Infusion solution bag
420,620‧‧‧隔壁 420, 620‧‧‧ next door
431‧‧‧輸注液袋本體 431‧‧‧Infusion bag body
432‧‧‧口栓構件 432‧‧‧port plug component
433‧‧‧吊掛孔 433‧‧‧Hanging hole
50‧‧‧擠壓塗覆層合裝置 50‧‧‧Extrusion coating lamination device
51‧‧‧擠壓機 51‧‧‧Extruder
52‧‧‧T模 52‧‧‧T
53‧‧‧冷卻滾筒 53‧‧‧cooling drum
54‧‧‧橡膠滾筒 54‧‧‧Rubber roller
501‧‧‧層合物 501‧‧‧Laminate
502‧‧‧樹脂薄膜 502‧‧‧Resin film
503‧‧‧層合薄膜(多層結構體) 503‧‧‧Laminated film (multilayer structure)
601,602‧‧‧真空隔熱體 601,602‧‧‧vacuum insulation
410a,410b,631,632‧‧‧薄膜材料 410a, 410b, 631, 632‧‧‧ film materials
651,652‧‧‧芯材 651,652‧‧‧Core material
[圖1]有關本發明之實施形態之一的縱製袋填充密封袋之概略圖。 [Fig. 1] A schematic diagram of a vertical bag-filled sealed bag according to an embodiment of the present invention.
[圖2]有關本發明之實施形態之一的平袋(flat pouch)之概略圖。 [Fig. 2] A schematic diagram of a flat pouch according to one embodiment of the present invention.
[圖3]有關本發明之實施形態之一的輸注液袋(bag)之模式圖。 [Fig. 3] A schematic diagram of an infusion solution bag according to one embodiment of the present invention.
[圖4]有關本發明之實施形態之一的模內標籤(In Mold Labeling)容器之模式圖。 [Fig. 4] A schematic diagram of an In Mold Labeling container according to an embodiment of the present invention.
[圖5]有關本發明之實施形態之一的多層結構體之製造所使用的擠壓塗覆層合裝置之一部份模式的斜視圖。 [Fig. 5] A perspective view of a partial mode of an extrusion coating lamination device used in the manufacture of a multilayer structure according to one embodiment of the present invention.
[圖6]有關本發明之實施形態之一的真空隔熱體之模 式圖。 [Fig. 6] A mold of a vacuum heat insulator according to an embodiment of the present invention Style diagram.
[圖7]有關本發明之實施形態之一的真空隔熱體之其他模式圖。 [Fig. 7] Another schematic diagram of a vacuum heat insulator according to an embodiment of the present invention.
[圖8]有關本發明之實施形態之一的電子裝置之部份截面圖。 [Fig. 8] A partial cross-sectional view of an electronic device according to one embodiment of the present invention.
本發明,將列舉以下例示進行說明。又,以下之說明中,雖有例示物質、條件、方法、數值範圍等之情形,但本發明並不受該些例示所限定。又,所例示之物質,於無特別註釋之情形,皆可單獨使用1種,或將2種以上合併使用。 The present invention will be explained with the following examples. In the following description, although there are cases where substances, conditions, methods, numerical ranges, etc. are exemplified, the present invention is not limited by these examples. In addition, the exemplified substances can be used alone or in combination of two or more without special notes.
於無特別註釋時,本說明書中,記載為「於特定構件(基材、層等)上層合特定之層」之意義中,除與該構件接觸方式層合該特定之層的情形之外,亦包含於挾夾有其他層之該構件上方層合該特定之層之情形。「特定構件(基材、層等)上形成特定之層」、「特定構件(基材、層等)上配置特定之層」之記載亦具有相同之意義。又,於無特別註釋時,「於特定構件(基材、層等)上塗佈液體(塗覆液等)」之記載的意義,除於該構件上直接塗佈該液體的情形以外,亦包含於該構件上所形成之其他層上塗佈該液體之情形。 When there is no special note, in this specification, it is described as "laminating a specific layer on a specific member (substrate, layer, etc.)", except for the case where the specific layer is laminated in contact with the member, It also includes the case where the specific layer is laminated on the member sandwiched by other layers. The descriptions of "a specific layer is formed on a specific member (substrate, layer, etc.)" and "a specific layer is arranged on a specific member (substrate, layer, etc.)" also have the same meaning. In addition, when there is no special note, the meaning of the description of "coating liquid (coating liquid, etc.) on a specific member (substrate, layer, etc.)", except for the case where the liquid is directly coated on the member, Including the case where the liquid is coated on other layers formed on the member.
本說明書中,會具有如「層(Y)」般,附有符號(Y)之層(Y),以與其他之層區別之情形。於無特別註釋 時,符號(Y)並不具有技術性之意義。基材(X)、化合物(A)及其他符號亦為相同之情形。但,如氫原子(H)般,明確標示特定元素之情形除外。 In this manual, there will be a layer (Y) with a symbol (Y) like "layer (Y)" to distinguish it from other layers. Yu No Special Notes At this time, the symbol (Y) does not have technical significance. The same applies to the substrate (X), compound (A) and other symbols. However, like the hydrogen atom (H), except when the specific element is clearly marked.
本發明之多層結構體,為含有基材(X)與含鋁之層(Y)。層(Y),為含有含鋁之化合物(A)(以下,亦僅稱為「化合物(A)」)與聚乙烯醇系樹脂之磷酸酯化物(BP)(以下,亦僅稱為「磷酸酯化物(BP)」),前述聚乙烯醇系樹脂之磷酸酯化物(BP)之磷酸酯化率RBP為0.15以上。以下之說明中,於無特別註釋時,「多層結構體」之文句為表示含有基材(X)與層(Y)之多層結構體之意。 The multilayer structure of the present invention includes a substrate (X) and an aluminum-containing layer (Y). The layer (Y) contains an aluminum-containing compound (A) (hereinafter, also simply referred to as "compound (A)") and a phosphate ester (BP) of a polyvinyl alcohol-based resin (hereinafter, also simply referred to as "phosphoric acid Ester (BP)"), the phosphate esterification rate R BP of the phosphate ester (BP) of the polyvinyl alcohol-based resin is 0.15 or more. In the following description, unless otherwise noted, the phrase "multilayer structure" means a multilayer structure containing a substrate (X) and a layer (Y).
層(Y)中,化合物(A)中之至少一部份與磷酸酯化物(BP)中之至少一部份可進行反應。又,層(Y)中含有無機磷化合物(BI)之情形,化合物(A)中之至少一部份與無機磷化合物(BI)及/或磷酸酯化物(BP)中之至少一部份可進行反應。層(Y)中之化合物(A)產生反應之情形,構成反應產物之化合物(A)的部份亦視為化合物(A)。該情形中,形成反應產物所使用之化合物(A)之質量(反應前之化合物(A)之質量),為包含於層(Y)中之化合物(A)之質量中。又,層(Y)與無機磷化合物(BI)及/或磷酸酯化物(BP)產生反應之情形,構成反應產物之無機磷化合物(BI)及/或磷酸酯化物(BP)之部份視為無機磷化合物(BI)及/或磷酸酯化物(BP)。該情形中,形成反應產物所使用之無機磷化合 物(BI)及/或磷酸酯化物(BP)之質量(反應前之無機磷化合物(BI)及/或磷酸酯化物(BP)之質量),包含於層(Y)中之無機磷化合物(BI)及/或磷酸酯化物(BP)之質量。 In the layer (Y), at least a part of the compound (A) and at least a part of the phosphate ester (BP) can react. Furthermore, when the layer (Y) contains an inorganic phosphorus compound (BI), at least a part of the compound (A) and at least a part of the inorganic phosphorus compound (BI) and/or phosphate ester (BP) may be React. In the case where the compound (A) in the layer (Y) reacts, the part of the compound (A) constituting the reaction product is also regarded as the compound (A). In this case, the mass of the compound (A) used to form the reaction product (the mass of the compound (A) before the reaction) is included in the mass of the compound (A) in the layer (Y). In addition, in the case where the layer (Y) reacts with the inorganic phosphorus compound (BI) and/or phosphate ester (BP), part of the inorganic phosphorus compound (BI) and/or phosphate ester (BP) constituting the reaction product is regarded as It is inorganic phosphorus compound (BI) and/or phosphate ester (BP). In this case, the inorganic phosphorus compound used to form the reaction product (BI) and/or phosphate ester (BP) mass (inorganic phosphorus compound (BI) and/or phosphate ester (BP) mass before reaction), the inorganic phosphorus compound contained in the layer (Y) ( BI) and/or phosphate ester (BP) quality.
基材(X)之材質,並未有特別之限定,其可使用各種材質所形成之基材。基材(X)之材質,例如,熱塑性樹脂、熱硬化性樹脂等樹脂;布帛、紙類等纖維集合體;木材;玻璃等。該些之中,又以熱塑性樹脂及纖維集合體為佳,以熱塑性樹脂為較佳。基材(X)之形態,並未有特別之限定,亦可為薄膜或薄片等層狀者。基材(X),以含有由熱塑性樹脂薄膜及紙所成群所選出之至少1種為佳,以含有熱塑性樹脂薄膜者為較佳,以熱塑性樹脂薄膜為更佳。 The material of the substrate (X) is not particularly limited, and substrates formed of various materials can be used. The material of the base material (X) is, for example, resins such as thermoplastic resins and thermosetting resins; fiber aggregates such as cloth and paper; wood; glass, etc. Among these, thermoplastic resins and fiber assemblies are more preferable, and thermoplastic resins are more preferable. The form of the base material (X) is not particularly limited, and it may be a layered film or sheet. The base material (X) preferably contains at least one selected from the group consisting of thermoplastic resin films and paper, preferably contains thermoplastic resin films, and more preferably thermoplastic resin films.
基材(X)所使用之熱塑性樹脂,例如,聚乙烯、聚丙烯等聚烯烴系樹脂;聚對苯二甲酸乙二酯(PET)、聚2,6-萘二甲酸乙二酯、聚對苯二甲酸丁二酯或該些之共聚物等聚酯系樹脂;尼龍-6、尼龍-66、尼龍-12等聚醯胺系樹脂;聚乙烯醇、乙烯-乙烯醇共聚物等含羥基之聚合物;聚苯乙烯;聚(甲基)丙烯酸酯;聚丙烯腈;聚乙酸乙烯酯;聚碳酸酯;聚丙烯酸酯;再生纖維素;聚醯亞胺;聚醚醯亞胺;聚碸;聚醚碸;聚醚醚酮;離子聚合物樹脂等。多層結構體作為包裝材料使用之情形,基材(X)之材料,以由聚乙烯、聚丙烯、聚對苯二甲酸乙二 酯、尼龍-6,及尼龍-66所成群所選出之至少1種的熱塑性樹脂為佳。 Thermoplastic resin used for the base material (X), for example, polyolefin resins such as polyethylene and polypropylene; polyethylene terephthalate (PET), polyethylene 2,6-naphthalene dicarboxylate, poly Polyester resins such as butylene phthalate or copolymers of these; polyamide resins such as nylon-6, nylon-66, nylon-12; and hydroxyl-containing resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers Polymer; Polystyrene; Poly(meth)acrylate; Polyacrylonitrile; Polyvinyl acetate; Polycarbonate; Polyacrylate; Regenerated cellulose; Polyimide; Polyetherimide; Polyphenol; Polyether ballast; polyether ether ketone; ionic polymer resin, etc. When the multilayer structure is used as a packaging material, the material of the base material (X) is made of polyethylene, polypropylene, polyethylene terephthalate At least one thermoplastic resin selected from the group consisting of ester, nylon-6, and nylon-66 is preferred.
前述熱塑性樹脂所形成之薄膜作為上述基材(X)使用之情形,基材(X)可為延伸薄膜亦可、無延伸薄膜亦可。就所得多層結構體具有優良加工適性(印刷或層合等)之觀點,以延伸薄膜,特別是二軸延伸薄膜為佳。二軸延伸薄膜,可為由同時二軸延伸法、逐次二軸延伸法,及管狀(tubular)延伸法之任一方法所製得之二軸延伸薄膜皆可。 When the film formed from the thermoplastic resin is used as the substrate (X), the substrate (X) may be a stretched film or may not be a stretched film. From the viewpoint that the resulting multilayer structure has excellent processability (printing, lamination, etc.), the stretched film, particularly the biaxially stretched film is preferred. The biaxially stretched film may be a biaxially stretched film made by any of the simultaneous biaxial stretching method, the sequential biaxial stretching method, and the tubular stretching method.
基材(X)所使用之紙,例如,圖畫紙、上質紙、模造紙、玻璃紙、羊皮紙、合成紙、白板紙、馬尼拉紙、奶瓶用紙(milk carton)原紙、杯(用)原紙、象牙紙等。使用紙作為基材(X)使用時,可製得紙容器用的多層結構體。 The paper used for the substrate (X), for example, drawing paper, fine paper, molded paper, cellophane, parchment, synthetic paper, whiteboard paper, manila paper, milk carton base paper, cup base paper, ivory paper Wait. When paper is used as the substrate (X), a multilayer structure for paper containers can be produced.
基材(X)為層狀時,其厚度,就所得多層結構體具有良好的機械性強度及加工性等觀點,以1~1,000μm為佳,以5~500μm為較佳,以9~200μm為更佳。 When the base material (X) is a layer, its thickness is preferably 1 to 1,000 μm, preferably 5 to 500 μm, and preferably 9 to 200 μm from the viewpoint that the resulting multilayer structure has good mechanical strength and processability. For better.
層(Y),為含有化合物(A)與磷酸酯化物(BP)。化合物(A)為含鋁之化合物。又,層(Y),以再含有無機磷化合物(BI)為佳。無機磷化合物(BI)及磷酸酯化物(BP),為具有含有磷原子之官能基。化合物(A)、無機磷化合物(BI),及 磷酸酯化物(BP)之內容將於以下說明。 The layer (Y) contains the compound (A) and the phosphate ester (BP). Compound (A) is a compound containing aluminum. In addition, it is preferable that the layer (Y) further contains an inorganic phosphorus compound (BI). Inorganic phosphorus compounds (BI) and phosphate esters (BP) have functional groups containing phosphorus atoms. Compound (A), inorganic phosphorus compound (BI), and The content of phosphate ester (BP) will be described below.
化合物(A),可為含鋁之金屬氧化物(Aa)亦可、含有由含鋁之金屬氧化物(Aa)(以下亦簡稱為「金屬氧化物(Aa)」)與無機磷化合物(BI)進行反應而得之反應產物(D)的化合物(Ab)(以下,亦稱為「化合物(Ab)」)亦可。 The compound (A) may be an aluminum-containing metal oxide (Aa) or may include an aluminum-containing metal oxide (Aa) (hereinafter also referred to as "metal oxide (Aa)") and an inorganic phosphorus compound (BI ) Compound (Ab) (hereinafter, also referred to as "compound (Ab)") of the reaction product (D) obtained by the reaction may also be used.
含鋁之金屬氧化物(Aa),通常,為以粒子形態與無機磷化合物(BI)進行反應。 The aluminum-containing metal oxide (Aa) usually reacts with the inorganic phosphorus compound (BI) in the form of particles.
構成含鋁之金屬氧化物(Aa)之金屬原子(該些亦有統稱為「金屬原子(M)」之情形),為由周期表之第2~14族所屬之金屬原子所選出之至少1種的金屬原子,但至少包含鋁。金屬原子(M)可單獨為鋁,或含有鋁與其以外的金屬原子亦可。又,金屬氧化物(Aa),可將2種以上的金屬氧化物(Aa)合併使用。 The metal atoms constituting the metal oxide (Aa) containing aluminum (these are also collectively referred to as "metal atoms (M)") are at least 1 selected from the metal atoms belonging to groups 2 to 14 of the periodic table Kind of metal atoms, but at least contains aluminum. The metal atom (M) may be aluminum alone, or may contain aluminum and other metal atoms. Furthermore, for the metal oxide (Aa), two or more kinds of metal oxides (Aa) can be used in combination.
金屬原子(M)所佔之比例,通常為50莫耳%以上,亦可為60~100莫耳%,或80~100莫耳%皆可。金屬氧化物(Aa)之例中,例如,包含由液相合成法、氣相合成法、固體粉碎法等方法而製得之金屬氧化物。 The proportion of metal atoms (M) is usually 50 mol% or more, and can also be 60-100 mol%, or 80-100 mol%. Examples of the metal oxide (Aa) include, for example, metal oxides prepared by methods such as liquid-phase synthesis, gas-phase synthesis, and solid pulverization.
金屬氧化物(Aa),可為含有鍵結於可水解之特性基之金屬原子(M)的化合物(E)之水解縮合物。該特性基之例,例如,包含後述通式〔I〕之R1。化合物(E)之水 解縮合物,實質上可視為金屬氧化物。因此,本說明書中,化合物(E)之水解縮合物亦有稱為「金屬氧化物(Aa)」之情形。即,本說明書中,「金屬氧化物(Aa)」可以解讀為「化合物(E)之水解縮合物」,又,「化合物(E)之水解縮合物」可以解讀為「金屬氧化物(Aa)」。 The metal oxide (Aa) may be a hydrolyzed condensate of a compound (E) containing a metal atom (M) bonded to a hydrolyzable characteristic group. Examples of this characteristic base include, for example, R 1 of the general formula [I] described later. The hydrolyzed condensate of compound (E) can be regarded as a metal oxide substantially. Therefore, in this specification, the hydrolyzed condensate of compound (E) may also be referred to as "metal oxide (Aa)". That is, in this specification, "metal oxide (Aa)" can be interpreted as "hydrolysis condensate of compound (E)", and "hydrolysis condensate of compound (E)" can be interpreted as "metal oxide (Aa)"".
就容易控制與無機磷化合物(BI)之反應機制、使所得多層結構體之氣體阻隔性更為優良之觀點,化合物(E),以含有下述通式〔I〕所表示之化合物(Ea)之至少1種為佳。 From the viewpoint of easily controlling the reaction mechanism with the inorganic phosphorus compound (BI) and making the gas barrier properties of the resulting multilayer structure more excellent, the compound (E) contains the compound (Ea) represented by the following general formula [I] At least one of them is preferred.
Al(R1)k(R2)3-k 〔I〕 Al(R 1 ) k (R 2 ) 3-k 〔I〕
式中,R1為,鹵素原子(氟原子、氯原子、溴原子、碘原子)、NO3、可具有取代基之碳數1~9之烷氧基、可具有取代基之碳數2~9之醯氧基、可具有取代基之碳數3~9之烯氧基、可具有取代基之碳數5~15之β-二酮基,或具有可具有取代基之碳數1~9之醯基的二醯甲基。R2為,可具有取代基之碳數1~9之烷基、可具有取代基之碳數7~10之芳烷基、可具有取代基之碳數2~9之烯基,或可具有取代基之碳數6~10之芳基。k為1~3之整數。R1存在多數之情形,R1可互相為相同亦可、相 異亦可。R2存在多數之情形,R2可互相為相同亦可、相異亦可。 In the formula, R 1 is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO 3 , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and a carbon number 2 to 2 which may have a substituent Acetyloxy group of 9, C3-C9 alkenyloxy group which may have a substituent, β-diketone group which may have a carbon number of 5-15, or C1-C9 which may have a substituent The diacyl group of the acyl group. R 2 is an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 9 carbon atoms which may have a substituent, or may have The aryl group having 6 to 10 carbon atoms in the substituent. k is an integer from 1 to 3. There are cases where most of the R 1, R 1 may be the same as each other, also different. R 2 is present the majority of circumstances, each of R 2 may be the same or, different also.
化合物(E),除化合物(Ea)以外,可含有至少一種下述通式〔II〕所表示之化合物(Eb)。 The compound (E), in addition to the compound (Ea), may contain at least one compound (Eb) represented by the following general formula [II].
M1(R3)m(R4)n-m 〔II〕 M 1 (R 3 ) m (R 4 ) nm 〔II〕
式中,M1為,鋁原子以外的金屬原子,且為由周期表之第2~14族所屬金屬原子所選出之至少1種的金屬原子。R3為,鹵素原子(氟原子、氯原子、溴原子、碘原子)、NO3、可具有取代基之碳數1~9之烷氧基、可具有取代基之碳數2~9之醯氧基、可具有取代基之碳數3~9之烯氧基、可具有取代基之碳數5~15之β-二酮基,或具有可具有取代基之碳數1~9之醯基的二醯甲基。R4為,可具有取代基之碳數1~9之烷基、可具有取代基之碳數7~10之芳烷基、可具有取代基之碳數2~9之烯基,或可具有取代基之碳數6~10之芳基。m為1~n之整數。n表示M1之原子價。R3存在多數之情形,R3可互相為相同亦可、相異亦可。R4存在多數之情形,R4可互相為相同亦可、相異亦可。 In the formula, M 1 is a metal atom other than an aluminum atom, and is at least one kind of metal atom selected from the metal atoms belonging to groups 2 to 14 of the periodic table. R 3 is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), NO 3 , an alkoxy group having 1 to 9 carbon atoms which may have a substituent, and an alkoxy group having 2 to 9 carbon atoms which may have a substituent Oxygen group, optionally substituted C3-C9 alkenyloxy group, optionally substituted C5-C15 di-keto group, or optionally substituted C1-C9 acetyl group Of diacylmethyl. R 4 is an alkyl group having 1 to 9 carbon atoms which may have a substituent, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 9 carbon atoms which may have a substituent, or may have The aryl group having 6 to 10 carbon atoms in the substituent. m is an integer from 1 to n. n represents the valence of M 1 . R 3 is present the majority of circumstances, each of R 3 may be the same or, different also. R 4 is present the majority of circumstances, each of R 4 may be the same or, different also.
R1及R3之烷氧基,例如,甲氧基、乙氧基、n-丙氧基、異丙氧基、n-丁氧基、異丁氧基、sec-丁氧基、tert-丁氧基、苄氧基、二苯基甲氧基、三苯甲氧基、4-甲氧基苄氧基、甲氧基甲氧基、1-乙氧基乙氧基、苄氧 基甲氧基、2-三甲基矽烷基乙氧基、2-三甲基矽烷基乙氧基甲氧基、苯氧基、4-甲氧基苯氧基等。 The alkoxy groups of R 1 and R 3 are, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert- Butoxy, benzyloxy, diphenylmethoxy, triphenylmethoxy, 4-methoxybenzyloxy, methoxymethoxy, 1-ethoxyethoxy, benzyloxymethoxy Oxy, 2-trimethylsilylethoxy, 2-trimethylsilylethoxymethoxy, phenoxy, 4-methoxyphenoxy, etc.
R1及R3之醯氧基,例如,乙醯氧基、乙基羰氧基、n-丙基羰氧基、異丙基羰氧基、n-丁基羰氧基、異丁基羰氧基、sec-丁基羰氧基、tert-丁基羰氧基、n-辛基羰氧基等。 Acyloxy of R 1 and R 3 , for example, acetyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyl Oxygen, sec-butylcarbonyloxy, tert-butylcarbonyloxy, n-octylcarbonyloxy, etc.
R1及R3之烯氧基,例如,烯丙氧基、2-丙烯氧基、2-丁烯氧基、1-甲基-2-丙烯氧基、3-丁烯氧基、2-甲基-2-丙烯氧基、2-戊烯氧基、3-戊烯氧基、4-戊烯氧基、1-甲基-3-丁烯氧基、1,2-二甲基-2-丙烯氧基、1,1-二甲基-2-丙烯氧基、2-甲基-2-丁烯氧基、3-甲基-2-丁烯氧基、2-甲基-3-丁烯氧基、3-甲基-3-丁烯氧基、1-乙烯基-2-丙烯氧基、5-己烯氧基等。 The alkenyloxy groups of R 1 and R 3 are , for example, allyloxy, 2-propenyloxy, 2-butenyloxy, 1-methyl-2-propenyloxy, 3-butenyloxy, 2- Methyl-2-propenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-3-butenyloxy, 1,2-dimethyl- 2-propenyloxy, 1,1-dimethyl-2-propenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 2-methyl-3 -Butenyloxy, 3-methyl-3-butenyloxy, 1-vinyl-2-propenyloxy, 5-hexenyloxy and the like.
R1及R3之β-二酮基,例如,2,4-戊烷二酮基、1,1,1-三氟-2,4-戊烷二酮基、1,1,1,5,5,5-六氟-2,4-戊烷二酮基、2,2,6,6-四甲基-3,5-庚烷二酮基、1,3-丁烷二酮基、2-甲基-1,3-丁烷二酮基、2-甲基-1,3-丁烷二酮基、苯甲醯基丙酮基等。 Β-diketone of R 1 and R 3 , for example, 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5 ,5,5-Hexafluoro-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-butanedione, 2-methyl-1,3-butanedione, 2-methyl-1,3-butanedione, benzoylacetone, etc.
R1及R3之二醯甲基之醯基,例如,甲醯基、乙醯基、丙醯基(Propanoyl基)、丁醯基(丁醯基)、戊醯基(Pentanoyl基)、己醯基等碳數1~6之脂肪族醯基;苯甲醯基、甲苯醯基等芳香族醯基(芳醯基)等。 Carbonyl groups of bis-methyl groups of R 1 and R 3 , for example, carbon groups such as methyl group, ethyl group, propyl group (Propanoyl group), butyl group (butyl group), pentyl group (Pentanoyl group), hexyl group, etc. Number 1~6 aliphatic acyl groups; aromatic acyl groups such as benzoyl acyl group, tolyl acyl group (aromatic acyl group), etc.
R2及R4之烷基,例如,甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n- 戊基、異戊基、n-己基、異己基、3-甲基戊基、2-甲基戊基、1,2-二甲基丁基、環丙基、環戊基、環己基等。 R 2 and R 4 alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, Isoamyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1,2-dimethylbutyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.
R2及R4之芳烷基,例如,苄基、苯基乙基(苯乙基)等。 The aralkyl groups of R 2 and R 4 are , for example, benzyl, phenylethyl (phenethyl) and the like.
R2及R4之烯基,例如,乙烯基、1-丙烯基、2-丙烯基、異丙烯基、3-丁烯基、2-丁烯基、1-丁烯基、1-甲基-2-丙烯基、1-甲基-1-丙烯基、1-乙基-1-乙烯基、2-甲基-2-丙烯基、2-甲基-1-丙烯基、3-甲基-2-丁烯基、4-戊烯基等。 Alkenyl groups of R 2 and R 4 , for example, vinyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 2-butenyl, 1-butenyl, 1-methyl -2-propenyl, 1-methyl-1-propenyl, 1-ethyl-1-vinyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, 3-methyl -2-butenyl, 4-pentenyl, etc.
R2及R4之芳基,例如,苯基、1-萘基、2-萘基等。 The aryl groups of R 2 and R 4 are , for example, phenyl, 1-naphthyl, 2-naphthyl and the like.
R1、R2、R3及R4中之取代基,例如,碳數1~6之烷基;甲氧基、乙氧基、n-丙氧基、異丙氧基、n-丁氧基、異丁氧基、sec-丁氧基、tert-丁氧基、n-戊氧基、異戊氧基、n-己氧基、環丙氧基、環丁氧基、環戊氧基、環己氧基等碳數1~6之烷氧基;甲氧基羰基、乙氧基羰基、n-丙氧基羰基、異丙氧基羰基、n-丁氧基羰基、異丁氧基羰基、sec-丁氧基羰基、tert-丁氧基羰基、n-戊氧羰基、異戊氧羰基、環丙氧羰基、環丁氧羰基、環戊氧羰基等碳數1~6之烷氧基羰基;苯基、甲苯基基、萘基等芳香族烴基;氟原子、氯原子、溴原子、碘原子等鹵素原子;碳數1~6之醯基;碳數7~10之芳烷基;碳數7~10之芳烷氧基;碳數1~6之烷胺基;具有碳數1~6之烷基之二烷胺基等。 Substituents in R 1 , R 2 , R 3 and R 4 , for example, C 1-6 alkyl; methoxy, ethoxy, n-propoxy, isopropoxy, n -butoxy Group, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy , Cyclohexyloxy and other alkoxy groups having 1 to 6 carbon atoms; methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Alkoxy groups with 1 to 6 carbon atoms such as carbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentyloxycarbonyl, etc. Carbonyl; aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl groups with 1 to 6 carbon atoms; aralkyl groups with 7 to 10 carbon atoms ; Aralkyloxy groups with carbon number 7-10; alkylamino groups with carbon number 1-6; dialkylamino groups with alkyl groups with carbon number 1-6, etc.
R1及R3,以鹵素原子、NO3、可具有取代基之碳數1~6之烷氧基、可具有取代基之碳數2~6之醯氧基、可具有取代基之碳數5~10之β-二酮基,或具有可具有取代基之碳數1~6之醯基之二醯甲基為佳,以可具有取代基之碳數1~6之烷氧基為較佳。 R 1 and R 3 are halogen atoms, NO 3 , alkoxy groups having 1 to 6 carbon atoms which may have substituents, alkoxy groups having 2 to 6 carbon atoms which may have substituents, and carbon numbers which may have substituents 5~10 β-diketone group, or a bismethyl group having 1 to 6 carbon groups that may have a substituent is preferred, and a 1 to 6 carbon alkoxy group that may have a substituent is preferred good.
R2及R4,以可具有取代基之碳數1~6之烷基為佳。式〔I〕之k,較佳為3。 R 2 and R 4 are preferably a C 1-6 alkyl group which may have a substituent. K of formula [I] is preferably 3.
M1,以周期表之第4族所屬之金屬原子為佳,以鈦、鋯為較佳。M1為周期表之第4族所屬之金屬原子的情形,式〔II〕之m,較佳為4。 M 1 is preferably a metal atom belonging to Group 4 of the periodic table, preferably titanium or zirconium. M 1 is the case of the metal atom to which Group 4 of the periodic table belongs, and m in formula [II] is preferably 4.
又,硼及矽雖有被分類為半金屬之情形,但本說明書中,該些為包含於金屬之中。 In addition, although boron and silicon may be classified as semi-metals, in this specification, these are included in metals.
化合物(Ea),例如,氯化鋁、硝酸鋁、乙酸鋁、參(2,4-戊烷二酮)鋁、三甲氧基鋁、三乙氧基鋁、三-n-丙氧基鋁、三異丙氧基鋁、三-n-丁氧基鋁、三-sec-丁氧基鋁、三-tert-丁氧基鋁等,其中,又以三異丙氧基鋁及三-sec-丁氧基鋁為佳。化合物(E),可將2種以上之化合物(Ea)合併使用。 Compound (Ea), for example, aluminum chloride, aluminum nitrate, aluminum acetate, ginseng (2,4-pentanedione) aluminum, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, Aluminum triisopropoxide, aluminum tri-n-butoxy, aluminum tri-sec-butoxy, aluminum tri-tert-butoxy, etc. Among them, aluminum triisopropoxide and aluminum tri-sec- Aluminum butoxide is preferred. Compound (E) can be used in combination of two or more compounds (Ea).
化合物(Eb),例如,四(2,4-戊烷二酮)鈦、四甲氧基鈦、四乙氧基鈦、四異丙氧基鈦、四-n-丁氧基鈦、四(2-乙基己氧基)鈦等鈦化合物;四(2,4-戊烷二酮)鋯、四-n-丙氧基鋯、四-n-丁氧基鋯等鋯化合物等。該些可單獨使用1種,或將2種以上之化合物(Eb)合併使用亦可。 Compound (Eb), for example, tetrakis(2,4-pentanedione) titanium, tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetrakis( Titanium compounds such as 2-ethylhexyloxy) titanium; zirconium compounds such as zirconium tetrakis(2,4-pentanedione), zirconium tetra-n-propoxy, zirconium tetra-n-butoxy, etc. One of these may be used alone, or two or more compounds (Eb) may be used in combination.
化合物(E)中,只要為可達成本發明效果之範圍,化合物(E)中化合物(Ea)所佔之比例並未有特別之限定。化合物(Ea)以外之化合物(例如,化合物(Eb))於化合物(E)中所佔之比例,例如,以20莫耳%以下為佳,以10莫耳%以下為較佳,以5莫耳%以下為更佳,亦可為0莫耳%。 In the compound (E), the ratio of the compound (Ea) in the compound (E) is not particularly limited as long as the effect of the invention can be achieved. The proportion of compounds other than compound (Ea) (for example, compound (Eb)) in compound (E), for example, preferably 20 mol% or less, preferably 10 mol% or less, 5 mol Ear% or less is better, or 0 mole %.
化合物(E)經由水解時,可使化合物(E)所具有的可水解之特性基中之至少一部份變換為羥基。此外,該水解物經由縮合時,可形成金屬原子(M)介由氧原子(O)鍵結而得之化合物。重複該縮合反應時,可形成實質上被視為金屬氧化物的化合物。又,依此方法所形成的金屬氧化物(Aa)之表面,通常存在有羥基。 When the compound (E) is hydrolyzed, at least a part of the hydrolyzable characteristic group possessed by the compound (E) can be converted into a hydroxyl group. In addition, when the hydrolyzate is condensed, it can form a compound in which a metal atom (M) is bonded via an oxygen atom (O). When this condensation reaction is repeated, a compound substantially regarded as a metal oxide can be formed. In addition, the surface of the metal oxide (Aa) formed by this method usually has hydroxyl groups.
本說明書中,〔僅鍵結於金屬原子(M)的氧原子(O)之莫耳數〕/〔金屬原子(M)之莫耳數〕之比為0.8以上之化合物,視為包含於金屬氧化物(Aa)中者。其中,僅鍵結於金屬原子(M)的氧原子(O),為M-O-M所表示之構造中之氧原子(O),M-O-H所表示之構造中之氧原子(O)般,與金屬原子(M)與氫原子(H)鍵結之氧原子則不包含於其中。金屬氧化物(Aa)中之上述比例,以0.9以上為佳,以1.0以上為較佳,以1.1以上為更佳。該比例之上限並未有特別之限定,但一般以金屬原子(M)之原子價為n時,通常以n/2表示。 In this specification, a compound whose ratio of [the number of moles of oxygen atoms (O) bonded only to metal atoms (M)]/[the number of moles of metal atoms (M)] is 0.8 or more is considered to be included in the metal Oxide (Aa). Among them, only the oxygen atom (O) bonded to the metal atom (M) is the oxygen atom (O) in the structure represented by MOM, and the oxygen atom (O) in the structure represented by MOH, and the metal atom ( M) The oxygen atom bonded to the hydrogen atom (H) is not included. The above ratio in the metal oxide (Aa) is preferably 0.9 or more, preferably 1.0 or more, and more preferably 1.1 or more. The upper limit of this ratio is not particularly limited, but generally when the valence of the metal atom (M) is n, it is usually expressed as n/2.
為啟動前述水解縮合反應,化合物(E)具有可水解之特性基為重要之條件。未鍵結該些基之情形,會造 成不易引起水解縮合反應或反應極為緩慢之情形,而極不容易製作目的物之金屬氧化物(Aa)。 In order to start the aforementioned hydrolysis condensation reaction, it is an important condition that the compound (E) has a hydrolyzable characteristic group. If these bases are not bonded, it will cause It is difficult to cause hydrolysis condensation reaction or the reaction is extremely slow, and it is extremely difficult to produce the target metal oxide (Aa).
化合物(E)之水解縮合物,例如,可使用公知之溶膠凝膠法之方法而由特定之原料製得。該原料,可使用由化合物(E)、化合物(E)之部份水解物、化合物(E)之完全水解物、化合物(E)中部份水解縮合而形成之化合物,及化合物(E)之完全水解物中之一部份經縮合而形成之化合物所成群所選出之至少1種。 The hydrolyzed condensate of the compound (E) can be prepared from a specific raw material using a known sol-gel method, for example. As the raw material, the compound (E), the partial hydrolysate of the compound (E), the complete hydrolysate of the compound (E), the compound formed by partial hydrolysis and condensation of the compound (E), and the compound (E) At least one selected from the group of compounds formed by condensation of a part of the complete hydrolysate.
可提供作為與含有無機磷化合物(BI)之物(無機磷化合物(BI),或,含有無機磷化合物(BI)之組成物)進行混合之金屬氧化物(Aa),以實質上不含有磷原子者為佳。 Metal oxide (Aa) can be provided as a mixture with a substance containing inorganic phosphorus compound (BI) (inorganic phosphorus compound (BI), or a composition containing inorganic phosphorus compound (BI)) so as not to contain phosphorus substantially Atom is better.
化合物(Ab)中所含之反應產物(D),為由金屬氧化物(Aa)與無機磷化合物(BI)進行反應而得者。其中,金屬氧化物(Aa)與無機磷化合物(BI)再與其他化合物進行反應所生成之化合物亦包含於反應產物(D)中。又,化合物(Ab)中,可含有一部份與反應無關之金屬氧化物(Aa)及/或無機磷化合物(BI)。 The reaction product (D) contained in the compound (Ab) is obtained by reacting the metal oxide (Aa) and the inorganic phosphorus compound (BI). Among them, the compound formed by the reaction of the metal oxide (Aa) and the inorganic phosphorus compound (BI) with other compounds is also included in the reaction product (D). In addition, the compound (Ab) may contain a part of the metal oxide (Aa) and/or the inorganic phosphorus compound (BI) not related to the reaction.
化合物(Ab)中,構成金屬氧化物(Aa)之金屬原子與由無機磷化合物(BI)產生之磷原子之莫耳比,以〔構成金屬氧化物(Aa)之金屬原子〕:〔由無機磷化合物(BI)產生之磷原子〕=1.0:1.0~3.6:1.0之範圍為佳,以 1.1:1.0~3.0:1.0之範圍為較佳。於此範圍外時,將會降低氣體阻隔性能。化合物(Ab)中之該莫耳比,可由形成化合物(Ab)之塗覆液中之金屬氧化物(Aa)與無機磷化合物(BI)之混合比例予以調整。化合物(Ab)中之該莫耳比,通常與塗覆液中之比例為相同。 In the compound (Ab), the molar ratio of the metal atom constituting the metal oxide (Aa) and the phosphorus atom produced by the inorganic phosphorus compound (BI) is [metal atom constituting the metal oxide (Aa)]: [from inorganic Phosphorus atom produced by phosphorus compound (BI)】=1.0: 1.0~3.6: 1.0 is better, The range of 1.1:1.0~3.0:1.0 is better. Outside this range, the gas barrier performance will be reduced. The molar ratio in the compound (Ab) can be adjusted by the mixing ratio of the metal oxide (Aa) and the inorganic phosphorus compound (BI) in the coating solution forming the compound (Ab). The molar ratio in the compound (Ab) is usually the same as the ratio in the coating liquid.
層(Y)之紅外線吸收圖譜中,800~1,400cm-1之區域中的最大吸收波數以1,080~1,130cm-1之範圍為佳。金屬氧化物(Aa)與無機磷化合物(BI)進行反應而形成反應產物(D)之過程中,由金屬氧化物(Aa)產生之金屬原子(M)與由無機磷化合物(BI)產生之磷原子(P),介由氧原子(O)而形成由M-O-P所表示之鍵結。其結果,於反應產物(D)之紅外線吸收圖譜中,將會生成由該鍵結產生之特性吸收帶。本發明者們經研究結果,發現以M-O-P之鍵結為基礎之特性吸收帶出現於1,080~1,130cm-1之區域時,可使所得多層結構體顯示出優良之氣體阻隔性。特別是,該特性吸收帶出現於一般為出現於各種之原子與氧原子鍵結而產生之吸收的800~1,400cm-1之區域中為最強吸收之情形時,得知可使所得多層結構體顯示出更優良之氣體阻隔性。 Infrared layer (Y) of the absorption spectrum, the maximum absorption wave number region of 800 ~ 1,400cm -1 is preferably in the range of 1,080 ~ 1,130cm -1. During the reaction between the metal oxide (Aa) and the inorganic phosphorus compound (BI) to form the reaction product (D), the metal atom (M) produced by the metal oxide (Aa) and the inorganic phosphorus compound (BI) Phosphorus atom (P) forms a bond represented by MOP via oxygen atom (O). As a result, in the infrared absorption spectrum of the reaction product (D), a characteristic absorption band due to the bonding will be generated. The inventors found through research that the characteristic absorption band based on the MOP bond appears in the region of 1,080~1,130 cm -1 , and the resulting multilayer structure can show excellent gas barrier properties. In particular, when the characteristic absorption band occurs in the region of 800~1,400cm -1 where absorption occurs when various atoms bond with oxygen atoms, it is known that the multilayer structure can be obtained. Shows better gas barrier properties.
相對於此,使烷氧金屬或金屬鹽等金屬化合物與無機磷化合物(BI)預先混合後,再進行水解縮合之情形中,可得到由金屬化合物產生之金屬原子與由無機磷化合物(BI)產生之磷原子,以幾乎均勻混合下進行反應而得之複合體。為該情形時,於紅外線吸收圖譜中,800~ 1,400cm-1之區域中之最大吸收波數為遠離於1,080~1,130cm-1之範圍。 On the other hand, when a metal compound such as an alkoxy metal or a metal salt is preliminarily mixed with an inorganic phosphorus compound (BI) and then hydrolyzed and condensed, a metal atom generated from the metal compound and an inorganic phosphorus compound (BI) can be obtained Phosphorus atoms produced are reacted with almost uniform mixing. In this case, in the infrared absorption spectrum, the maximum absorption wavenumber in the region of 800 to 1,400 cm -1 is far from the range of 1,080 to 1,130 cm -1 .
層(Y)之紅外線吸收圖譜中,800~1,400cm-1之區域中之最大吸收帶之半高寬值(FWHM),就所得多層結構體之氣體阻隔性之觀點,以200cm-1以下為佳,以150cm-1以下為較佳,以100cm-1以下為更佳,以50cm-1以下為特佳。 Infrared layer (Y) of the absorption spectrum, the half width of 800 to a maximum value of absorption band in the region of 1,400cm -1 (the FWHM), the viewpoint of the gas barrier property of the resultant multilayer structure, the following is to 200cm -1 Preferably, it is preferably 150 cm -1 or less, more preferably 100 cm -1 or less, and particularly preferably 50 cm -1 or less.
層(Y)之紅外線吸收圖譜可依實施例所記載之方法進行測定。但,實施例所記載之方法無法進行測定時,亦可使用反射吸收法、外部反射法、衰減全反射法等反射測定、由多層結構體採取層(Y)、石蠟糊法(nujol mull method)、錠劑法等透過測定等方法進行測定亦可,但並不僅限定於該些方法。 The infrared absorption pattern of layer (Y) can be measured according to the method described in the examples. However, when the method described in the examples cannot be measured, reflection measurement such as reflection absorption method, external reflection method, attenuation total reflection method, layer (Y) from a multilayer structure, and nujol mull method can also be used , Lozenge, etc. may be measured by methods such as measurement, but it is not limited to these methods.
化合物(Ab)中,金屬氧化物(Aa)之粒子相互間,亦可具有介由無機磷化合物(BI)產生之磷原子而鍵結之構造。作為化合物(Ab)之原料使用之金屬氧化物(Aa)之粒子,於形成化合物(Ab)之過程中,可改變形狀或尺寸。 In the compound (Ab), the particles of the metal oxide (Aa) may have a structure in which phosphorus atoms generated by the inorganic phosphorus compound (BI) are bonded. The particles of the metal oxide (Aa) used as the raw material of the compound (Ab) can change the shape or size during the formation of the compound (Ab).
無機磷化合物(BI)為含有可與金屬氧化物(Aa)進行反應之部位,典型上,為含有多數個該類之部位。無機磷化合物(BI),以含有2~20個該類之部位(原子團或官能基)的化合物為佳。該類之部位之例示中,為包含可與存在於金屬氧化物(Aa)之表面的官能基(例如,羥基)進行縮合反 應之部位。該類之部位,例如,直接鍵結於磷原子之鹵素原子、直接鍵結於磷原子之氧原子等。存在於金屬氧化物(Aa)之表面的官能基(例如,羥基),通常為鍵結於構成金屬氧化物(Aa)之金屬原子(M)。 The inorganic phosphorus compound (BI) contains a site that can react with the metal oxide (Aa), and typically contains many such sites. The inorganic phosphorus compound (BI) is preferably a compound containing 2 to 20 such sites (atomic groups or functional groups). Examples of such sites include condensation reaction with functional groups (for example, hydroxyl groups) present on the surface of the metal oxide (Aa) Should be. Such sites include, for example, halogen atoms directly bonded to phosphorus atoms and oxygen atoms directly bonded to phosphorus atoms. The functional group (for example, hydroxyl group) present on the surface of the metal oxide (Aa) is usually bonded to the metal atom (M) constituting the metal oxide (Aa).
無機磷化合物(BI),例如,磷酸、二磷酸、三磷酸、4分子以上之磷酸縮合而得之聚磷酸、亞磷酸、膦酸、亞膦酸、膦酸、亞膦酸等磷之含氧酸,及該些之鹽(例如,磷酸鈉),與該些之衍生物(例如,鹵化物(例如,氯化磷醯基)、脫水物(例如,五氧化二磷))等。 Inorganic phosphorus compounds (BI), such as phosphoric acid, phosphorous acid, phosphorous acid, phosphonic acid, phosphonic acid, phosphonic acid, phosphonic acid, etc. Acids, and these salts (for example, sodium phosphate), derivatives of these (for example, halides (for example, phosphoramidyl chloride), dehydrates (for example, phosphorus pentoxide)), and the like.
該些無機磷化合物(BI),可單獨使用1種亦可、將2種以上合併使用亦可。該些無機磷化合物(BI)之中,又以單獨使用磷酸,或將磷酸與其以外的無機磷化合物(BI)合併使用者為佳。使用磷酸時,可提高後述塗覆液(S)之安定性與所得多層結構體之氣體阻隔性。合併使用磷酸與其以外的無機磷化合物(BI)之情形,以無機磷化合物(BI)中之50莫耳%以上為磷酸者為佳。 These inorganic phosphorus compounds (BI) may be used alone or in combination of two or more. Among these inorganic phosphorus compounds (BI), it is preferable to use phosphoric acid alone or to combine phosphoric acid with other inorganic phosphorus compounds (BI). When phosphoric acid is used, the stability of the coating liquid (S) described later and the gas barrier properties of the resulting multilayer structure can be improved. In the case of using phosphoric acid together with an inorganic phosphorus compound (BI) other than that, it is preferable that 50 mol% or more of the inorganic phosphorus compound (BI) is phosphoric acid.
本發明之多層結構體,除聚乙烯醇系樹脂之磷酸酯化物(BP)以外,以不含有含磷原子之聚合物(BO)者為佳。含磷原子之聚合物(BO)所具有之含磷原子之官能基,例如,磷酸基、亞磷酸(phosphonous acid)基、膦酸(Phosphonic acid)基、亞膦酸(Phosphonous acid)基、膦酸(Phosphonic acid)基、亞膦酸(Phosphonous acid)基,及該些所衍生之 官能基(例如,鹽、(部份)酯化合物、鹵化物(例如,氯化物)、脫水物)等。含磷原子之聚合物(BO),例如,含有10個以上磷原子之高分子化合物等。 The multilayer structure of the present invention is preferably one that does not contain a phosphorus atom-containing polymer (BO) other than the phosphate ester (BP) of the polyvinyl alcohol-based resin. Phosphorus atom-containing functional groups of the phosphorus atom-containing polymer (BO), for example, phosphoric acid group, phosphorous acid (phosphonous acid) group, phosphonic acid (Phosphonic acid) group, phosphorous acid (Phosphonous acid) group, phosphine Phosphonic acid group, Phosphonous acid group, and those derived from them Functional groups (for example, salts, (partial) ester compounds, halides (for example, chlorides), dehydrates), and the like. The phosphorus atom-containing polymer (BO) is, for example, a polymer compound containing more than 10 phosphorus atoms.
多層結構體可再含有無機蒸鍍層。無機蒸鍍層可將無機物經由蒸鍍而形成。無機物,例如,金屬(例如,鋁)、金屬氧化物(例如,氧化矽、氧化鋁)、金屬氮化物(例如,氮化矽)、金屬氮化氧化物(例如,酸氮化矽),或金屬碳化氮化物(例如,碳氮化矽)等。該些之中,又以氧化鋁、氧化矽、氧化鎂,或氮化矽所形成之無機蒸鍍層,就對氧或水蒸氣具有優良阻隔性之觀點,而為較佳。本發明之多層結構體中之層(Y),可含有含鋁之無機蒸鍍層。例如,層(Y),亦可含有鋁之蒸鍍層(Ac)及/或氧化鋁之蒸鍍層(Ad)。 The multilayer structure may further contain an inorganic vapor-deposited layer. The inorganic vapor-deposited layer can be formed by vapor-depositing an inorganic substance. Inorganic substances, for example, metals (for example, aluminum), metal oxides (for example, silicon oxide, aluminum oxide), metal nitrides (for example, silicon nitride), metal nitride oxides (for example, acid silicon nitride), or Metal carbide nitride (for example, silicon carbonitride) and the like. Among them, the inorganic vapor-deposited layer formed of aluminum oxide, silicon oxide, magnesium oxide, or silicon nitride is preferable from the viewpoint of having excellent barrier properties against oxygen or water vapor. The layer (Y) in the multilayer structure of the present invention may contain an inorganic vapor-deposited layer containing aluminum. For example, the layer (Y) may also contain a vapor-deposited layer (Ac) of aluminum and/or a vapor-deposited layer (Ad) of aluminum oxide.
無機蒸鍍層之形成方法,並未有特別之限定、真空蒸鍍法(例如,電阻加熱蒸鍍、電子束蒸鍍、分子線磊晶法等)、濺鍍法、離子鍍敷法等物理氣相成長法、熱化學氣相成長法(例如,觸媒化學氣相成長法)、光化學氣相成長法、電漿化學氣相成長法(例如,容量鍵結電漿、感應耦合式電漿、表面波電漿、電子迴旋加速共振、雙磁控濺鍍(dual-magnetron)、原子層堆積法等)、有機金屬氣相成長法等化學氣相成長法。 The method of forming the inorganic vapor deposition layer is not particularly limited, such as vacuum vapor deposition method (for example, resistance heating vapor deposition, electron beam vapor deposition, molecular wire epitaxy method, etc.), sputtering method, ion plating method and other physical gases Phase growth method, thermal chemical vapor growth method (for example, catalyst chemical vapor growth method), photochemical vapor growth method, plasma chemical vapor growth method (for example, capacity bonding plasma, inductively coupled plasma) , Surface wave plasma, electron cyclotron resonance, dual-magnetron sputtering (dual-magnetron), atomic layer deposition method, etc.), organic metal vapor growth method and other chemical vapor growth methods.
無機蒸鍍層之厚度,依構成無機蒸鍍層之成 份的種類而有所相異,一般以0.002~0.5μm為佳,以0.005~0.2μm為較佳,以0.01~0.1μm為更佳。可於此範圍內,選擇具有良好之多層結構體的阻隔性或機械性物性的厚度即可。無機蒸鍍層之厚度未達0.002μm時,會有降低對於氧或水蒸氣的無機蒸鍍層之阻隔性的重現性之傾向,又,無機蒸鍍層也會有未能產生充分之阻隔性的情形。又,無機蒸鍍層之厚度超過0.5μm時,將多層結構體拉伸或彎曲時,無機蒸鍍層之阻隔性也會有降低之傾向。 The thickness of the inorganic vapor-deposited layer depends on the composition of the inorganic vapor-deposited layer The type of serving varies, generally 0.002 to 0.5 μm is preferred, 0.005 to 0.2 μm is preferred, and 0.01 to 0.1 μm is more preferred. Within this range, it is sufficient to select a thickness having good barrier properties or mechanical properties of the multilayer structure. When the thickness of the inorganic vapor-deposited layer is less than 0.002 μm, there is a tendency to reduce the reproducibility of the barrier property to the inorganic vapor-deposited layer of oxygen or water vapor. In addition, the inorganic vapor-deposited layer may fail to produce sufficient barrier properties. . In addition, when the thickness of the inorganic vapor-deposited layer exceeds 0.5 μm, the barrier property of the inorganic vapor-deposited layer tends to decrease when the multilayer structure is stretched or bent.
聚乙烯醇系樹脂之磷酸酯化物(BP),為將聚乙烯醇系樹脂與磷酸經酯化而製得。聚乙烯醇系樹脂,例如,聚乙烯醇、聚乙酸乙烯酯之部份皂化物、乙烯-乙烯醇共聚物、乙烯-乙酸乙烯酯共聚物之部份皂化物等,其中,又以聚乙烯醇、乙烯-乙烯醇共聚物為佳,以聚乙烯醇為較佳。前述磷酸酯化物(BP),以含有下述通式〔III〕所表示之磷酸酯化乙烯醇單位15.0~99.8莫耳%者為特佳。就生產性之觀點,磷酸酯化乙烯醇單位之含量以99.0莫耳%以下為較佳,以95.0莫耳%以下為更佳。又,就可製得具有優良層間接著力之多層結構體之觀點,磷酸酯化乙烯醇單位之含量以30.0莫耳%以上為較佳,以45.0莫耳%以上為更佳,以60.0莫耳%以上為特佳。 The phosphate ester compound (BP) of the polyvinyl alcohol resin is prepared by esterifying the polyvinyl alcohol resin and phosphoric acid. Polyvinyl alcohol-based resins, for example, polyvinyl alcohol, partial saponification of polyvinyl acetate, ethylene-vinyl alcohol copolymer, partial saponification of ethylene-vinyl acetate copolymer, etc. Among them, polyvinyl alcohol Ethylene-vinyl alcohol copolymer is preferred, with polyvinyl alcohol being preferred. The aforementioned phosphate ester (BP) is particularly preferably one containing 15.0 to 99.8 mol% of phosphorylated vinyl alcohol unit represented by the following general formula [III]. From the viewpoint of productivity, the content of phosphorylated vinyl alcohol units is preferably 99.0 mol% or less, and more preferably 95.0 mol% or less. In addition, from the viewpoint of obtaining a multilayer structure having excellent interlayer adhesion, the content of phosphated vinyl alcohol unit is preferably 30.0 mol% or more, more preferably 45.0 mol% or more, and 60.0 mol. More than% is particularly good.
[化2]
本發明所使用之聚乙烯醇系樹脂之皂化度,以75.0~99.85莫耳%為佳,就可製得具有優良層間接著力之多層結構體之觀點,以80.0~99.5莫耳%為較佳,以85.0~99.3莫耳%為更佳,以90.0~99.1莫耳%為特佳。皂化度,為依JIS K 6726(1994年)所求得之值。 The saponification degree of the polyvinyl alcohol-based resin used in the present invention is preferably from 75.0 to 99.85 mol%, and from the viewpoint of producing a multilayer structure having excellent interlayer adhesion, 80.0 to 99.5 mol% is preferred , 85.0~99.3 mol% is better, and 90.0~99.1 mol% is especially good. The degree of saponification is a value obtained in accordance with JIS K 6726 (1994).
本發明所使用之聚乙烯醇系樹脂之黏度平均聚合度,以100~4,000為佳,就可製得具有優良層間接著力之多層結構體之觀點,以200~3,500為較佳,以300~3,000為更佳,以500~2,800為特佳。黏度平均聚合度,為依JIS K 6726(1994年)所求得之值。 The average polymerization degree of viscosity of the polyvinyl alcohol-based resin used in the present invention is preferably from 100 to 4,000, from the viewpoint of producing a multilayer structure with excellent interlayer adhesion, preferably from 200 to 3,500, preferably from 300 to 3,000 is better, 500~2,800 is especially good. The average polymerization degree of viscosity is a value obtained in accordance with JIS K 6726 (1994).
本發明所使用之聚乙烯醇系樹脂之黏度,以1.0~200mPa.s為佳,就可製得具有優良層間接著力之多層結構體之觀點,以3.0~150mPa.s為較佳,以11~90mPa.s為更佳,以20~85mPa.s為特佳。黏度,為依JIS K 6726(1994年)規定,於20℃下使用4質量%水溶液,以B型迴轉黏度計所測定之值。 The viscosity of the polyvinyl alcohol resin used in the present invention is 1.0 to 200 mPa. s is better, you can produce a multi-layer structure with excellent interlayer adhesion, from 3.0 to 150mPa. s is better, with 11~90mPa. s is better, with 20~85mPa. s is very good. Viscosity is the value measured with a B-type rotary viscometer using a 4 mass% aqueous solution at 20°C in accordance with JIS K 6726 (1994).
本發明所使用之聚乙烯醇系樹脂,其皂化度為85.0~99.3莫耳%,黏度平均聚合度為200~3,500,且黏度以11~90mPa.s者為佳,皂化度為85.0~99.3莫耳 %,黏度平均聚合度為500~2,800,且以黏度為20~85mPa‧s者為較佳。 The polyvinyl alcohol resin used in the present invention has a saponification degree of 85.0 to 99.3 mol%, an average viscosity degree of polymerization of 200 to 3,500, and a viscosity of 11 to 90 mPa. s is better, the saponification degree is 85.0~99.3 mole %, the average viscosity polymerization degree is 500~2,800, and the viscosity of 20~85mPa‧s is better.
磷酸酯化物(BP),只要可於多層結構體之製造過程中,形成磷酸酯基者即可。 Phosphate ester (BP) may be used as long as it can form a phosphate group in the manufacturing process of the multilayer structure.
為製得具有優良層間接著力之多層結構體,磷酸酯化物(BP)之磷酸酯化率RBP為0.15以上。又,就製得具有優良層間接著力之多層結構體之觀點,以0.24以上為佳,以0.37以上為較佳,以0.54以上為更佳。磷酸酯化率RBP,可依下式之聚乙烯醇系樹脂與磷酸進行酯化反應中,聚乙烯醇系樹脂與磷酸之添加量所算出之值。 To produce a multilayer structure having a high level of focus indirectly, phosphate compound (BP) of R BP phosphate ratio is 0.15 or more. From the viewpoint of producing a multilayer structure having excellent interlayer adhesion, 0.24 or more is preferable, 0.37 or more is more preferable, and 0.54 or more is more preferable. The phosphate esterification rate R BP can be calculated from the addition amount of the polyvinyl alcohol resin and phosphoric acid in the esterification reaction of the polyvinyl alcohol resin and phosphoric acid according to the following formula.
酯化率RBP={無機磷化合物(BI)添加量(g)/無機磷化合物(BI)之分子量}/〔{(皂化度/100)×聚乙烯醇系樹脂添加量(g)}/44.05〕 Esterification rate R BP = {inorganic phosphorus compound (BI) addition amount (g)/inorganic phosphorus compound (BI) molecular weight}/[{(saponification degree/100)×polyvinyl alcohol resin addition amount (g)}/ 44.05〕
聚乙烯醇系樹脂與磷酸添加量之比例(重量比),以聚乙烯醇系樹脂:磷酸=20:80~85:15為佳,以25:85~70:30為較佳,以30:70~65:35為更佳。 The ratio (weight ratio) of the addition amount of polyvinyl alcohol resin and phosphoric acid is preferably polyvinyl alcohol resin: phosphoric acid=20:80~85:15, preferably 25:85~70:30, preferably 30: 70~65:35 is better.
本發明之多層結構體所含之層(Y),可為僅由含鋁之化合物(A)、無機磷化合物(BI),及磷酸酯化物(BP)所構成者亦可;可為僅由含鋁之金屬氧化物(Aa)、無機磷化合物(BI),及磷酸酯化物(BP)所構成者亦可;可為僅由含有含鋁之金屬氧化物(Aa)與無機磷化合物(BI)之反應產物(D)的化合物(Ab)、無機磷化合物(BI),及磷酸酯化物(BP)所構成者亦可;可為僅由含鋁之金屬氧化物(Aa)、含有含鋁之金屬氧化物(Aa)與無機磷化合物(BI)之反應產物 (D)的化合物(Ab)、無機磷化合物(BI),及磷酸酯化物(BP)所構成者亦可。又,前述任一實施態樣中,層(Y)中可再含有其他之成份。其他之成份,例如,碳酸鹽、鹽酸鹽、硝酸鹽、碳酸氫鹽、硫酸鹽、硫酸氫鹽、硼酸鹽等無機酸金屬鹽;草酸鹽、乙酸鹽、酒石酸鹽、硬脂酸鹽等有機酸金屬鹽;環戊二烯基金屬錯合物(例如,二茂鈦)、氰基金屬錯合物(例如,普魯士藍)等金屬錯合物;層狀黏土化合物;交聯劑;高分子化合物(F):可塑劑;抗氧化劑;紫外線吸收劑;難燃劑等。多層結構體中之層(Y)中的前述其他成份之含有率,以50質量%以下為佳,以20質量%以下為較佳,以10質量%以下為更佳,以5質量%以下為特佳,亦可為0質量%(不含其他之成份)。 The layer (Y) contained in the multilayer structure of the present invention may be composed only of the aluminum-containing compound (A), the inorganic phosphorus compound (BI), and the phosphate ester (BP); it may be composed of only Aluminum-containing metal oxides (Aa), inorganic phosphorus compounds (BI), and phosphate esters (BP) may also be used; it may be composed only of aluminum-containing metal oxides (Aa) and inorganic phosphorus compounds (BI ) The reaction product (D) of the compound (Ab), the inorganic phosphorus compound (BI), and the phosphate ester (BP) may also be constituted; it may be composed only of the aluminum-containing metal oxide (Aa), containing aluminum The reaction product of metal oxide (Aa) and inorganic phosphorus compound (BI) (D) The compound (Ab), the inorganic phosphorus compound (BI), and the phosphate ester (BP) may be constituted. In addition, in any of the foregoing embodiments, the layer (Y) may further contain other components. Other ingredients, for example, carbonate, hydrochloride, nitrate, bicarbonate, sulfate, bisulfate, borate and other inorganic acid metal salts; oxalate, acetate, tartrate, stearate, etc. Organic acid metal salts; metal complexes such as cyclopentadienyl metal complexes (for example, titanocene), cyano metal complexes (for example, Prussian blue); layered clay compounds; crosslinking agents; high Molecular compound (F): plasticizer; antioxidant; ultraviolet absorber; flame retardant, etc. The content of the aforementioned other components in the layer (Y) in the multilayer structure is preferably 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass or less Very good, it can also be 0% by mass (excluding other ingredients).
如上述般,層(Y)可含有高分子化合物(F)。高分子化合物(F),例如,可具有由醚鍵結、羰基、羥基、羧基、羧酸酐基,及羧基之鹽所成群所選出之至少1種的官能基之聚合物(Fa)。 As described above, the layer (Y) may contain the polymer compound (F). The polymer compound (F) may have, for example, a polymer (Fa) having at least one functional group selected from the group consisting of an ether bond, a carbonyl group, a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, and a salt of a carboxyl group.
聚合物(Fa),例如,聚乙二醇;聚酮;聚乙烯醇、含有1~50莫耳%碳數4以下之α-烯烴單位之變性聚乙烯醇、聚乙烯縮醛(例如,聚乙烯縮丁醛)等聚乙烯醇系聚合物;纖維素、澱粉、環糊精等多糖類;聚(甲基)丙烯酸羥基乙基、聚(甲基)丙烯酸、乙烯-丙烯酸共聚物等(甲基)丙烯酸系聚合物;乙烯-馬來酸酐共聚物之水解物、苯 乙烯-馬來酸酐共聚物之水解物、異丁烯-馬來酸酐交互共聚物之水解物等馬來酸系聚合物等。該些之中,又以聚乙烯醇系聚合物為佳,具體而言,以聚乙烯醇及含有1~15莫耳%之碳數4以下的α-烯烴單位之變性聚乙烯醇為佳。 Polymer (Fa), for example, polyethylene glycol; polyketone; polyvinyl alcohol, denatured polyvinyl alcohol containing 1 to 50 mol% of α-olefin units with a carbon number of 4 or less, polyvinyl acetal (for example, poly (Vinyl butyral) and other polyvinyl alcohol polymers; cellulose, starch, cyclodextrin and other polysaccharides; poly(meth)acrylic acid hydroxyethyl, poly(meth)acrylic acid, ethylene-acrylic acid copolymer, etc. Base) acrylic polymer; hydrolysate of ethylene-maleic anhydride copolymer, benzene Maleic acid-based polymers such as hydrolysates of ethylene-maleic anhydride copolymers and isobutylene-maleic anhydride copolymers, etc. Among these, a polyvinyl alcohol-based polymer is more preferable, and specifically, a polyvinyl alcohol and a modified polyvinyl alcohol containing 1 to 15 mole% of α-olefin units having a carbon number of 4 or less are preferable.
聚合物(Fa),可為具有聚合性基之單體(例如,乙酸乙烯酯、丙烯酸)之均聚合物亦可、2種以上之單體的共聚物亦可,亦可為羥基及/或具有羧基之單體與不具有該基之單體所得之共聚物。又,聚合物(Fa),可合併使用2種以上之聚合物(Fa)。 The polymer (Fa) may be a homopolymer of a monomer having a polymerizable group (for example, vinyl acetate, acrylic acid), a copolymer of two or more monomers, or a hydroxyl group and/or A copolymer obtained by a monomer having a carboxyl group and a monomer having no such group. In addition, for the polymer (Fa), two or more kinds of polymers (Fa) can be used in combination.
聚合物(Fa)之分子量並未有特別之限制,就可得到具有更優良的氣體阻隔性及機械性強度之多層結構體之觀點,聚合物(Fa)之數平均分子量,以5,000以上為佳,以8,000以上為較佳,以10,000以上為更佳。聚合物(Fa)之數平均分子量之上限並未有特別之限定,例如,為1,500,000以下。 The molecular weight of the polymer (Fa) is not particularly limited. From the viewpoint of obtaining a multilayer structure having better gas barrier properties and mechanical strength, the number average molecular weight of the polymer (Fa) is preferably 5,000 or more. , More preferably 8,000 or more, more preferably 10,000 or more. The upper limit of the number average molecular weight of the polymer (Fa) is not particularly limited, and is, for example, 1,500,000 or less.
就使多層結構體保持良好外觀之觀點,層(Y)中之聚合物(Fa)之含量,於以層(Y)之質量作為基準(100質量%)時,以85質量%以下為佳,以50質量%以下為較佳,以20質量%以下為更佳,以10質量%以下為特佳。聚合物(Fa),可與層(Y)中之成份產生反應亦可、不產生反應者亦可。 From the viewpoint of maintaining a good appearance of the multilayer structure, the content of the polymer (Fa) in the layer (Y) is preferably 85% by mass or less when the mass of the layer (Y) is used as a reference (100% by mass). It is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The polymer (Fa) may react with the components in the layer (Y), or it may not react.
層(Y)之厚度(多層結構體具有2層以上之層(Y)時,各層(Y)厚度之合計),以0.05~4.0μm之範圍為佳,以0.1~2.0μm之範圍為較佳。使層(Y)薄化時,於印刷、 層合等加工時,可將多層結構體之尺寸變化抑制至更低。又,因可增加多層結構體之柔軟性,其力學特性將可趨近基材本身之力學特性。本發明之多層結構體具有2層以上之層(Y)時,就氣體阻隔性之觀點,每一層(Y)的厚度以0.05μm以上為佳。層(Y)之厚度,可使用形成層(Y)所使用之後述塗覆液(T)之濃度或其塗佈方法予以控制。 The thickness of the layer (Y) (when the multilayer structure has more than two layers (Y), the total thickness of each layer (Y)) is preferably in the range of 0.05 to 4.0 μm, preferably in the range of 0.1 to 2.0 μm . When thinning the layer (Y), the printing, During processing such as lamination, the dimensional change of the multilayer structure can be suppressed to a lower level. Furthermore, since the flexibility of the multilayer structure can be increased, its mechanical properties can approach the mechanical properties of the substrate itself. When the multilayer structure of the present invention has two or more layers (Y), from the viewpoint of gas barrier properties, the thickness of each layer (Y) is preferably 0.05 μm or more. The thickness of the layer (Y) can be controlled using the concentration of the coating liquid (T) described later used for forming the layer (Y) or its coating method.
層(Y)之厚度,可使用掃瞄型電子顯微鏡或穿透型電子顯微鏡觀察多層結構體之截面方式予以測定。 The thickness of the layer (Y) can be determined by observing the cross-section of the multilayer structure using a scanning electron microscope or a transmission electron microscope.
因本發明之多層結構體之說明事項可適用於本發明之製造方法中,故以下會有省略重複說明之部份。又,本發明之製造方法之說明事項,亦適用於本發明之多層結構體。 Since the descriptions of the multilayer structure of the present invention can be applied to the manufacturing method of the present invention, the repeated description will be omitted below. In addition, the description of the manufacturing method of the present invention is also applicable to the multilayer structure of the present invention.
本發明之多層結構體之製造方法,例如包含,前驅體層形成步驟(i)、含有磷酸酯化物(BP)之塗覆液(T)之塗佈步驟(ii),及氣體阻隔層(Y)之形成步驟(iii)之製造方法等。又,化合物(A)、無機磷化合物(BI)、磷酸酯化物(BP),及該些之質量比之內容,係如上所述,於製造方法中將省略重複之說明。 The manufacturing method of the multilayer structure of the present invention includes, for example, a precursor layer forming step (i), a coating solution (T) containing a phosphate ester (BP) coating step (ii), and a gas barrier layer (Y) The manufacturing method of the forming step (iii), etc. In addition, the content of the compound (A), the inorganic phosphorus compound (BI), the phosphate ester (BP), and these mass ratios are as described above, and repeated explanations will be omitted in the manufacturing method.
步驟(i)為,將含有含鋁之化合物(A)的塗覆液(S)塗佈於基材(X)上,而於基材(X)上形成層(Y)之前驅體層。經 由步驟(i),可製得含有基材(X)與層(Y)之前驅體層的結構體。層(Y)為含有鋁之蒸鍍層(Ac),或氧化鋁之蒸鍍層(Ad)之情形,該些之層可依上述一般蒸鍍法形成。因此,以下將詳細說明含有化合物(Ab)之層(Y1)之前驅體層的形成方法。 Step (i) is to apply the coating liquid (S) containing the aluminum-containing compound (A) on the substrate (X), and form a layer (Y) precursor layer on the substrate (X). through From step (i), a structure containing the precursor layer of the substrate (X) and the layer (Y) can be prepared. The layer (Y) is in the case of a vapor-deposited layer (Ac) containing aluminum or a vapor-deposited layer (Ad) of aluminum oxide. These layers can be formed according to the general vapor deposition method described above. Therefore, the method of forming the precursor layer of the layer (Y1) containing the compound (Ab) will be described in detail below.
較佳之實施態樣為,塗覆液(S)(第1塗覆液),可將金屬氧化物(Aa)與無機磷化合物(BI)於溶劑中混合進行反應之方式可製得。具體而言,例如,塗覆液(S)為,將金屬氧化物(Aa)之分散液,與含有無機磷化合物(B1)之溶液進行混合之方法;於金屬氧化物(Aa)之分散液中添加、混合無機磷化合物(BI)之方法等而可製得。該些之混合時的溫度,以50℃以下為佳,以30℃以下為較佳,以20℃以下為更佳。塗覆液(S)中可含有其他之化合物(例如,高分子化合物(F)),必要時,可含有由乙酸、鹽酸、硝酸、三氟乙酸,及三氯乙酸所成之群所選出之至少1種的氧化合物(Q)。 A preferred embodiment is that the coating liquid (S) (first coating liquid) can be prepared by mixing and reacting the metal oxide (Aa) and the inorganic phosphorus compound (BI) in a solvent. Specifically, for example, the coating liquid (S) is a method of mixing a dispersion liquid of a metal oxide (Aa) with a solution containing an inorganic phosphorus compound (B1); a dispersion liquid of a metal oxide (Aa) It can be prepared by adding or mixing inorganic phosphorus compound (BI). The temperature during the mixing is preferably 50°C or lower, more preferably 30°C or lower, and even more preferably 20°C or lower. The coating liquid (S) may contain other compounds (for example, polymer compound (F)), and if necessary, may contain acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid. At least one oxygen compound (Q).
金屬氧化物(Aa)之分散液,例如,可依使用公知溶膠凝膠法之方法,例如,將化合物(E)、水,及必要時添加之酸觸媒或有機溶劑混合,使化合物(E)縮合或水解縮合而予製得。將化合物(E)縮合或水解縮合而製得金屬氧化物(Aa)之分散液時,必要時,可對所得分散液施以特定處理(於前述氧化合物(Q)之存在下之解膠等)等。所使用之溶劑並未有特別之限定,又以甲醇、乙醇、異丙醇等醇類;水;或該些之混合溶劑為佳。 The dispersion liquid of the metal oxide (Aa) can be, for example, a method using a known sol-gel method, for example, by mixing the compound (E), water, and an acid catalyst or organic solvent added if necessary to make the compound (E ) Condensation or hydrolysis condensation to prepare. When the compound (E) is condensed or hydrolytically condensed to obtain a dispersion of the metal oxide (Aa), if necessary, the resulting dispersion can be subjected to specific treatment (degumming in the presence of the aforementioned oxygen compound (Q), etc. )Wait. The solvent used is not particularly limited, and alcohols such as methanol, ethanol, and isopropanol; water; or mixed solvents of these are preferred.
含有無機磷化合物(BI)之溶液可將無機磷化合物(BI)溶解於溶劑之方式予以製作。溶劑,可配合無機磷化合物(BI)之種類作適當之選擇亦可,又以含有水者為佳。只要不會妨礙無機磷化合物(BI)之溶解時,溶劑亦可包含有機溶劑(例如,甲醇等醇類)。 The solution containing the inorganic phosphorus compound (BI) can be prepared by dissolving the inorganic phosphorus compound (BI) in a solvent. The solvent may be appropriately selected according to the type of inorganic phosphorus compound (BI), and it is better to contain water. As long as it does not hinder the dissolution of the inorganic phosphorus compound (BI), the solvent may include an organic solvent (for example, alcohols such as methanol).
塗覆液(S)之固形分濃度,就該塗覆液之保存安定性及對基材(X)之塗佈性之觀點,以1~20質量%為佳,以2~15質量%為較佳,以3~10質量%為更佳。前述固形分濃度,例如,可將餾除塗覆液(S)之溶劑後所殘存之固形分之質量,除以供處理之塗覆液(S)之質量的方式而計算出。 The solid concentration of the coating liquid (S) is preferably 1-20% by mass, and 2-15% by mass from the viewpoint of the storage stability of the coating liquid and the coating property to the substrate (X) Preferably, 3 to 10% by mass is more preferable. The aforementioned solid content concentration can be calculated, for example, by dividing the mass of the solid content remaining after distilling off the solvent of the coating liquid (S) by dividing the mass of the coating liquid (S) for treatment.
塗覆液(S),於使用布氏(Brookfield)迴轉黏度計(SB型黏度計:轉子No.3、迴轉速度60rpm)所測定之黏度,於塗佈時之溫度中,以3,000mPa.s以下為佳,以2,500mPa.s以下為較佳,以2,000mPa.s以下為更佳。該黏度為3,000mPa.s以下時,可提高塗覆液(S)之平整性,而製得具有更優良外觀之多層結構體。又,塗覆液(S)之黏度,以50mPa.s以上為佳,以100mPa.s以上為較佳,以200mPa.s以上為更佳。 The coating liquid (S), the viscosity measured using a Brookfield rotary viscosity meter (SB type viscometer: rotor No. 3, rotation speed 60rpm), at the temperature of the coating, at 3,000mPa. Below s is better, at 2,500mPa. Below s is better, with 2,000mPa. Below s is better. The viscosity is 3,000mPa. At s or less, the flatness of the coating liquid (S) can be improved, and a multilayer structure having a better appearance can be produced. In addition, the viscosity of the coating liquid (S) is 50 mPa. s is better than 100mPa. s above is better, with 200mPa. Above s is better.
塗覆液(S)中,並未有特別之限定,其中,鋁原子與磷原子之莫耳比,以鋁原子:磷原子=1.01:1.00~1.50:1.00為佳,以1.05:1.00~1.45:1.00為較佳。鋁原子與磷原子之莫耳比,可對塗覆液(S)之乾固物之進行螢光X線分析而可算出。 There is no particular limitation in the coating solution (S). Among them, the molar ratio of aluminum atoms to phosphorus atoms is preferably aluminum atoms: phosphorus atoms = 1.01: 1.00 to 1.50: 1.00, and 1.05: 1.00 to 1.45 : 1.00 is better. The molar ratio of aluminum atoms to phosphorus atoms can be calculated by fluorescent X-ray analysis of the dry solids of the coating liquid (S).
塗覆液(S),可直接塗佈於基材(X)之至少一側之面上,或介由其他之層(J)而塗佈於基材(X)上亦可。又,塗佈塗覆液(S)之前,可使用公知之固定塗覆劑處理基材(X)之表面,或於基材(X)之表面塗佈公知之接著劑等,而於基材(X)之表面形成接著層(I)亦可。 The coating liquid (S) may be directly coated on at least one side of the substrate (X), or may be coated on the substrate (X) through another layer (J). In addition, before applying the coating liquid (S), the surface of the substrate (X) may be treated with a known fixed coating agent, or a known adhesive agent or the like may be applied to the surface of the substrate (X). The adhesion layer (I) may be formed on the surface of (X).
塗覆液(S)之塗佈方法,並未有特別之限定,其可採用公知之方法。塗佈方法,例如,鑄模法、浸漬法、滾筒塗覆法、凹版塗佈法、網版印刷法、反向塗覆法、噴灑塗佈法、單面供膠塗佈法(kiss coat)法、擠壓塗佈法、熔融條狀塗佈法、密封式刮刀(chamber doctor)併用塗佈法、淋幕塗佈法、條狀塗佈法等。 The coating method of the coating liquid (S) is not particularly limited, and a known method can be used. Coating methods, for example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, single-side kiss coat method , Extrusion coating method, molten strip coating method, sealed doctor blade (chamber doctor) combined use coating method, curtain coating method, strip coating method, etc.
通常、步驟(i)中,經由去除塗覆液(S)中之溶劑的方式,而形成層(Y1)之前驅體層。去除溶劑之方法並未有特別之限制,其可使用公知之乾燥方法。乾燥方法,例如,熱風乾燥法、熱滾筒接觸法、紅外線加熱法、微波加熱法等。乾燥溫度,以基材(X)開始流動之溫度以下為佳。塗佈塗覆液(S)之後的乾燥溫度,例如,可為80~180℃左右亦可、90~150℃左右亦可。乾燥時間,並未有特別之限定,例如,以0.1秒鐘~1小時為佳,以1秒鐘~15分鐘為較佳,以5~300秒鐘為更佳。又,乾燥處理之後,以進行加熱處理為佳。加熱處理溫度,例如,可為100~200℃左右亦可、120~180℃左右亦可,但以高於乾燥溫度之溫度為佳。熱處理時間,並未有特別之限定,例如,熱處理之時間,以1秒鐘~1小時為佳,以1秒鐘~ 15分鐘為較佳,以5~300秒鐘為更佳。 Normally, in step (i), the precursor layer of the layer (Y1) is formed by removing the solvent in the coating liquid (S). The method for removing the solvent is not particularly limited, and a known drying method can be used. Drying methods, for example, hot air drying method, hot roller contact method, infrared heating method, microwave heating method and the like. The drying temperature is preferably below the temperature at which the base material (X) starts to flow. The drying temperature after applying the coating liquid (S) may be, for example, about 80 to 180°C, or about 90 to 150°C. The drying time is not particularly limited. For example, it is preferably 0.1 second to 1 hour, preferably 1 second to 15 minutes, and more preferably 5 to 300 seconds. Furthermore, it is preferable to perform heat treatment after drying treatment. The heat treatment temperature may be, for example, about 100 to 200°C or 120 to 180°C, but it is preferably a temperature higher than the drying temperature. The heat treatment time is not particularly limited. For example, the heat treatment time is preferably 1 second to 1 hour, and 1 second to 15 minutes is better, and 5 to 300 seconds is better.
步驟(ii)為,於步驟(i)所得之層(Y)之前驅體層上,塗佈含有磷酸酯化物(BP)之塗覆液(T)(第2塗覆液)。塗覆液(T),為將磷酸酯化物(BP)及溶劑混合而可製得。塗覆液(T)所使用之溶劑,可配合磷酸酯化物(BP)之種類作適當之選擇即可,並未有特別之限定,又以甲醇、乙醇、異丙醇等醇類;水;或該些之混合溶劑為佳。 Step (ii) is to apply a coating solution (T) (second coating solution) containing a phosphate ester (BP) on the precursor layer before the layer (Y) obtained in step (i). The coating liquid (T) can be prepared by mixing a phosphate ester (BP) and a solvent. The solvent used in the coating liquid (T) can be appropriately selected according to the type of phosphate ester (BP), and is not particularly limited, and alcohols such as methanol, ethanol, isopropanol, etc.; water; Or these mixed solvents are preferable.
塗覆液(T)中之固形分的濃度,就溶液之保存安定性或塗佈性之觀點,以0.01~60質量%為佳,以0.1~50質量%為較佳,以0.2~40質量%為更佳。固形分濃度,可依與有關塗覆液(S)之記載方法為相同之方法求得。又,就可達成本發明之效果之範圍,塗覆液(T)中,可含有上述層(Y)中所含之其他成份(例如,高分子化合物(F))。 The concentration of the solid content in the coating solution (T) is preferably 0.01 to 60% by mass, preferably 0.1 to 50% by mass, and 0.2 to 40% from the viewpoint of the storage stability or coating properties of the solution % Is better. The solid content concentration can be obtained by the same method as described in the coating liquid (S). In addition, as far as the effect of the invention can be achieved, the coating liquid (T) may contain other components (for example, the polymer compound (F)) contained in the layer (Y).
塗佈塗覆液(T)之後,經由去除溶劑處理,而形成層(Y)之前驅體層。與塗佈塗覆液(S)之相同般,塗佈塗覆液(T)之方法並未有特別之限定,而可採用公知之方法。 After applying the coating liquid (T), a solvent removal treatment is performed to form a layer (Y) precursor layer. As with the application of the coating liquid (S), the method of applying the coating liquid (T) is not particularly limited, and a known method can be used.
去除塗覆液(T)之溶劑的方法並未有特別之限定,其可使用公知之乾燥方法。乾燥方法,例如,熱風乾燥法、熱滾筒接觸法、紅外線加熱法、微波加熱法等。乾燥溫度,以基材(X)開始流動之溫度以下為佳。塗覆液(T) 之塗佈後的乾燥溫度,例如,可為90~240℃左右亦可,又以100~200℃為佳。 The method of removing the solvent of the coating liquid (T) is not particularly limited, and a known drying method can be used. Drying methods, for example, hot air drying method, hot roller contact method, infrared heating method, microwave heating method and the like. The drying temperature is preferably below the temperature at which the base material (X) starts to flow. Coating fluid (T) The drying temperature after coating may be, for example, about 90 to 240°C, and preferably 100 to 200°C.
步驟(iii)為,將步驟(i)及(ii)所形成之層(Y1)之前驅體層,於140℃以上之溫度下進行熱處理而形成層(Y1)。該熱處理溫度,以較塗佈塗覆液(T)之後的乾燥溫度為更高者為佳。 In step (iii), the precursor layer before the layer (Y1) formed in steps (i) and (ii) is heat-treated at a temperature of 140° C. or higher to form layer (Y1). The heat treatment temperature is preferably higher than the drying temperature after applying the coating liquid (T).
步驟(iii)為,使金屬氧化物(Aa)之粒子相互間,介由磷原子(由無機磷化合物(BI)產生之磷原子)進行鍵結反應。以另一觀點而言,步驟(iii)為進行反應產物(D)之生成反應。為使該反應得以充分進行,熱處理之溫度為140℃以上,又以170℃以上為佳,以180℃以上為較佳,以190℃以上為更佳。熱處理溫度過低時,為進行充分反應度時將需花費極長之時間,而為造成生產性降低之原因。熱處理溫度之較佳上限,依基材(X)之種類等而有所差異。例如,聚醯胺系樹脂所形成之熱塑性樹脂薄膜作為基材(X)使用之情形,熱處理之溫度以270℃以下為佳。又,聚酯系樹脂所形成之熱塑性樹脂薄膜作為基材(X)使用之情形,熱處理之溫度以240℃以下為佳。熱處理,可於空氣氛圍下、於氮氛圍下,氬氛圍下等予以實施。熱處理之時間,以0.1秒鐘~1小時為佳,以1秒鐘~15分鐘為較佳,以5~300秒鐘為更佳。 In the step (iii), the particles of the metal oxide (Aa) are bonded to each other via phosphorus atoms (phosphorus atoms produced by the inorganic phosphorus compound (BI)). From another point of view, step (iii) is to proceed to the formation reaction of the reaction product (D). In order to allow the reaction to proceed sufficiently, the temperature of the heat treatment is 140°C or higher, preferably 170°C or higher, preferably 180°C or higher, and more preferably 190°C or higher. When the heat treatment temperature is too low, it will take an extremely long time to perform a sufficient degree of reactivity, which is a cause of reduced productivity. The preferred upper limit of the heat treatment temperature varies depending on the type of substrate (X). For example, when a thermoplastic resin film formed of a polyamide-based resin is used as the substrate (X), the heat treatment temperature is preferably 270°C or lower. In addition, when the thermoplastic resin film formed of the polyester-based resin is used as the substrate (X), the temperature of the heat treatment is preferably 240° C. or lower. The heat treatment can be performed in an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like. The heat treatment time is preferably from 0.1 seconds to 1 hour, preferably from 1 second to 15 minutes, and more preferably from 5 to 300 seconds.
本發明之多層結構體之製造方法的較佳實施 態樣之一為,塗佈塗覆液(S)之後,進行乾燥處理(第1乾燥處理),隨後進行熱處理(第1熱處理)而形成前驅體層,於塗佈塗覆液(T)之後,進行乾燥處理(第2乾燥處理),隨後進行熱處理(第2熱處理)。此時,以前述第1熱處理之溫度較第1乾燥處理之溫度為更高、前述第2熱處理之溫度較第2乾燥處理之溫度為更高、前述第2熱處理之溫度較前述第1熱處理之溫度為更高者為佳。 The preferred implementation of the manufacturing method of the multilayer structure of the present invention One aspect is that, after applying the coating liquid (S), a drying process (first drying process) is performed, followed by heat treatment (first heat treatment) to form a precursor layer, and after applying the coating liquid (T), Drying treatment (second drying treatment) is performed, followed by heat treatment (second heat treatment). At this time, the temperature of the first heat treatment is higher than the temperature of the first drying treatment, the temperature of the second heat treatment is higher than the temperature of the second drying treatment, and the temperature of the second heat treatment is higher than the temperature of the first heat treatment The higher the temperature, the better.
本發明之多層結構體中,層(Y)與基材(X)可以直接接觸方式層合者亦可、層(Y)介由其他構件(例如,接著層(I)、其他之層(J))而層合於基材(X)而得者亦可。 In the multilayer structure of the present invention, the layer (Y) and the substrate (X) may be laminated in direct contact, and the layer (Y) may be interposed by other members (for example, the adhesion layer (I), other layers (J )) and those laminated on the substrate (X) are also acceptable.
本發明之多層結構體,例如,可將基材(X)直接或介由接著層(I)層合於層(Y)之後,再將其他層(J)以直接或介由接著層(I)以擠壓塗覆層合法形成之方式,而可再具有經由擠壓塗覆層合所形成之層。本發明所可使用之擠壓塗覆層合法並未有特別之限定,亦可使用公知之方法。典型之擠壓塗覆層合法,為將溶融之熱塑性樹脂送入T模中,將由T模之扁平槽縫取出之熱塑性樹脂冷卻處理後,即可製得層合薄膜。 The multilayer structure of the present invention can, for example, laminate the substrate (X) directly or via the adhesive layer (I) on the layer (Y), and then another layer (J) to directly or via the adhesive layer (I) ) In the way that the extrusion coating layer is legally formed, it may further have a layer formed by extrusion coating lamination. The law of the extrusion coating layer that can be used in the present invention is not particularly limited, and known methods can also be used. The typical extrusion coating method is to send the melted thermoplastic resin into the T-die and cool the thermoplastic resin taken out from the flat slot of the T-die to prepare a laminated film.
擠壓塗覆層合法中,最普通之單獨層合法之例示,將參照圖式說明如下。單獨層合法所使用之裝置之一例示係如圖5所示。又,圖5為僅顯示裝置的主要部份之模式圖,故與實際之裝置有所差異。圖5之裝置50,
為含有擠壓機51、T模52、冷卻滾筒53,及橡膠滾筒54。冷卻滾筒53及橡膠滾筒54,為以滾筒面互相接觸之狀態下配置。
In the extrusion coating layer method, the most common example of a separate layer method will be explained as follows with reference to the drawings. An example of a device used by a separate layer is shown in Figure 5. 5 is a schematic diagram showing only the main part of the device, so it is different from the actual device. The
熱塑性樹脂,於擠壓機內經加熱溶融,由T模52之扁平槽縫擠壓出,而形成樹脂薄膜502。另一方面,由薄片送出裝置(未於圖示中標示)送出層合物501,而與樹脂薄膜502同時挾夾於冷卻滾筒53與橡膠滾筒54之間。於冷卻滾筒53與橡膠滾筒54之間,層合物501與樹脂薄膜502以層合狀態被挾夾結果,而製得層合物501與樹脂薄膜502形成整體化之層合薄膜(多層結構體)503。
The thermoplastic resin is melted by heating in the extruder and extruded from the flat slot of the T-die 52 to form a
前述單獨層合法以外之擠壓塗覆層合法,例如,三明治層合法、串聯(tandem)層合法等。三明治層合法,為將溶融之熱塑性樹脂擠壓至一側之基材,由另外的拆捲機(unwinder)(捲出機)供應第2基材進行貼合,而製得層合物之方法。串聯層合法,為將單獨層合機以2台串聯而一次製作具有5層構成內容之層合物之方法。 Extrusion coating layer methods other than the aforementioned separate layer method, for example, sandwich layer method, tandem layer method, etc. Sandwich lamination is a method for preparing a laminate by extruding molten thermoplastic resin to a substrate on one side and supplying a second substrate from another unwinder (unwinder) for lamination . The tandem lamination method is a method for making a laminate having 5 layers of composition content by connecting two laminators in series at a time.
使用上述之層合物時,可製得一種於擠壓塗覆層合後亦可維持高阻隔性能,且可降低光透過性減低之多層結構體。 When the above-mentioned laminate is used, a multilayer structure that can maintain high barrier properties after extrusion coating lamination and can reduce light transmission can be prepared.
本發明之多層結構體中,使用接著層(I)時,會有提高基材(X)與層(Y)之接著性之情形。接著層(I),可由接著性 樹脂所構成者亦可。接著性樹脂所構成之接著層(I),可以使用公知之固定塗覆劑處理基材(X)表面之方式,或於基材(X)表面塗佈公知接著劑之方式予以形成。該接著劑,以由聚異氰酸酯成份與聚醇成份混合、反應之2液反應型聚胺基甲酸酯系接著劑為佳。又,固定塗覆劑或接著劑中,經由添加公知之矽烷耦合劑等少量添加劑之方式,會有使接著性再提高之情形。矽烷耦合劑,例如,具有異氰酸酯基、環氧基、胺基、脲基、氫硫基等反應性基之矽烷耦合劑等,但並不僅限定於該些內容。基材(X)與層(Y)介由接著層(I)而強力接著時,於對本發明之多層結構體進行印刷或層合等加工之際,可有效地抑制氣體阻隔性或外觀之惡化,此外,可提高使用本發明之多層結構體的包裝材料之落下強度。接著層(I)之厚度以0.01~10.0μm為佳,以0.03~5.0μm為較佳。 In the multilayer structure of the present invention, when the adhesive layer (I) is used, the adhesion between the substrate (X) and the layer (Y) may be improved. Next layer (I) Resin can also be used. The adhesive layer (I) composed of an adhesive resin can be formed by treating the surface of the substrate (X) with a known fixed coating agent or applying a known adhesive to the surface of the substrate (X). The adhesive is preferably a two-liquid reactive polyurethane adhesive which is a mixture and reaction of a polyisocyanate component and a polyol component. In addition, in the fixing coating agent or the adhesive, by adding a small amount of additives such as a well-known silane coupling agent, the adhesiveness may be further improved. The silane coupling agent is, for example, a silane coupling agent having reactive groups such as an isocyanate group, an epoxy group, an amine group, a urea group, and a hydrogen sulfide group, etc., but it is not limited to these contents. When the base material (X) and the layer (Y) are strongly bonded through the adhesive layer (I), when the multilayer structure of the present invention is printed or laminated, the deterioration of the gas barrier property or appearance can be effectively suppressed In addition, the drop strength of the packaging material using the multilayer structure of the present invention can be improved. The thickness of the next layer (I) is preferably from 0.01 to 10.0 μm, preferably from 0.03 to 5.0 μm.
本發明之多層結構體,就提高各種特性(例如,熱密封性、阻隔性、力學物性)之觀點,可含有其他之層(J)。該些本發明之多層結構體,例如,可將基材(X)直接或介由接著層(I)層合於層(Y)之後,再與其他之層(J)直接或介由接著層(I)進行接著或形成之方式予以製得。其他之層(J),例如,油墨層;聚烯烴層、乙烯-乙烯醇共聚物樹脂層等熱塑性樹脂層等,但並不僅限定於該內容。 The multilayer structure of the present invention may contain other layers (J) from the viewpoint of improving various characteristics (for example, heat sealability, barrier properties, and mechanical properties). For the multilayer structures of the present invention, for example, the substrate (X) can be laminated directly or via the adhesive layer (I) on the layer (Y), and then directly or via the adhesive layer with other layers (J) (I) It is made by way of continuation or formation. Other layers (J), for example, an ink layer; a polyolefin layer, a thermoplastic resin layer such as an ethylene-vinyl alcohol copolymer resin layer, etc., are not limited to this content.
本發明之多層結構體,可含有為印刷商品名 或圖樣等所使用的油墨層。該些本發明之多層結構體,例如,可將基材(X)直接或介由接著層(I)層合於層(Y)之後,再直接形成該油墨層之方式予以製得。油墨層,例如,將溶劑中分散有含有顏料(例如,二氧化鈦)之聚胺基甲酸酯樹脂的液體乾燥而得之被膜等,亦可為將不含顏料之聚胺基甲酸酯樹脂或其他樹脂作為主劑之油墨或電子電路配線形成用光阻乾燥而得之被膜。對層(Y)塗佈油墨層之方法,除凹版印刷法以外,又例如刮棒塗佈法、旋轉塗佈法、擠壓式塗佈法等各種塗佈方法。油墨層之厚度以0.5~10.0μm為佳,以1.0~4.0μm為較佳。 The multilayer structure of the present invention may contain a printed trade name Or the ink layer used for patterns, etc. The multilayer structures of the present invention can be prepared, for example, by laminating the substrate (X) directly or via the adhesive layer (I) on the layer (Y), and then directly forming the ink layer. The ink layer is, for example, a coating obtained by drying a liquid in which a polyurethane resin containing pigment (for example, titanium dioxide) is dispersed in a solvent, or a polyurethane resin containing no pigment or A film obtained by drying other resins as a main agent for ink or for forming photoresist for electronic circuit wiring. The method of applying the ink layer to the layer (Y) includes, in addition to the gravure printing method, various coating methods such as a bar coating method, a spin coating method, and an extrusion coating method. The thickness of the ink layer is preferably 0.5-10.0 μm, preferably 1.0-4.0 μm.
本發明之多層結構體中,磷酸酯化物(BP),因具有與化合物(A)具有高親和性之磷酸酯基,與,與接著層(I)或其他之層(J)具有高親和性之羥基等二者,故可提高層(Y)與其他之層的密著性。因此,即使殺菌處理後亦可維持層間接著力,而可抑制剝離等外觀不良之情形。 In the multilayer structure of the present invention, the phosphate ester (BP) has a phosphate group having a high affinity with the compound (A), and has a high affinity with the adhesive layer (I) or other layers (J) The hydroxyl group and the like can improve the adhesion between the layer (Y) and other layers. Therefore, even after the sterilization treatment, the interlayer adhesive force can be maintained, and the appearance defects such as peeling can be suppressed.
本發明之多層結構體之最表面層設定為聚烯烴層時,可賦予多層結構體熱密封性、提高多層結構體之力學特性等。就提高熱密封性或力學特性等觀點,聚烯烴以聚丙烯或聚乙烯為佳。又,就提高多層結構體之力學特性之目的,以層合由聚酯所形成之薄膜、聚醯胺所形成之薄膜,及含羥基之聚合物所形成之薄膜所成群所選出之至少1個薄膜者為佳。就提高力學特性之觀點,聚酯以聚對苯二甲酸乙二酯為佳,聚醯胺以尼龍-6為佳。又,就全層具有阻隔性之觀點,含羥基之聚合物以乙烯-乙烯醇共聚 物為佳。又,各層之間,於必要時,可設置固定塗覆層或接著劑所形成之層。 When the outermost layer of the multilayer structure of the present invention is a polyolefin layer, the multilayer structure can be given heat sealability, and the mechanical properties of the multilayer structure can be improved. From the viewpoint of improving heat sealability or mechanical properties, polypropylene or polyethylene is preferred. In addition, for the purpose of improving the mechanical properties of the multilayer structure, at least 1 selected from the group consisting of a film formed of polyester, a film formed of polyamide, and a film formed of a polymer containing hydroxyl groups A thin film is better. From the viewpoint of improving the mechanical properties, polyethylene terephthalate is preferred, and nylon-6 is preferred for polyamide. In addition, from the viewpoint that the entire layer has barrier properties, the hydroxyl group-containing polymer is copolymerized with ethylene-vinyl alcohol Good is better. In addition, between the layers, if necessary, a layer formed by a fixed coating layer or an adhesive may be provided.
本發明之多層結構體之構成的具體例係如以下所示。多層結構體,可具有基材(X)、層(Y)以外之其他構件(例如,接著層(I)、其他之層(J)),但於以下之具體例中,則省略其他構件之記載。又,以下具體例亦可進行複數層之層合或組合。 Specific examples of the structure of the multilayer structure of the present invention are shown below. Multi-layer structure may have other members (for example, adhesive layer (I), other layer (J)) other than the base material (X) and layer (Y), but in the following specific examples, the other members are omitted Record. In addition, in the following specific examples, a plurality of layers may be laminated or combined.
(1)層(Y)/聚酯層、(2)層(Y)/聚酯層/層(Y)、(3)層(Y)/聚醯胺層、(4)層(Y)/聚醯胺層/層(Y)、(5)層(Y)/聚烯烴層、(6)層(Y)/聚烯烴層/層(Y)、(7)層(Y)/含羥基之聚合物層、(8)層(Y)/含羥基之聚合物層/層(Y)、(9)層(Y)/紙層、(10)層(Y)/紙層/層(Y)、(11)層(Y)/無機蒸鍍層/聚酯層、(12)層(Y)/無機蒸鍍層/聚醯胺層、(13)層(Y)/無機蒸鍍層/聚烯烴層、(14)層(Y)/無機蒸鍍層/含羥基之聚合物層、(15)層(Y)/聚酯層/聚醯胺層/聚烯烴層、 (16)層(Y)/聚酯層/層(Y)/聚醯胺層/聚烯烴層、(17)聚酯層/層(Y)/聚酯層/層(Y)/無機蒸鍍層/含羥基之聚合物層/聚烯烴層、(18)聚酯層/層(Y)/聚醯胺層/聚烯烴層、(19)層(Y)/聚醯胺層/聚酯層/聚烯烴層、(20)層(Y)/聚醯胺層/層(Y)/聚酯層/聚烯烴層、(21)聚醯胺層/層(Y)/聚酯層/聚烯烴層、(22)層(Y)/聚烯烴層/聚醯胺層/聚烯烴層、(23)層(Y)/聚烯烴層/層(Y)/聚醯胺層/聚烯烴層、(24)聚烯烴層/層(Y)/聚醯胺層/聚烯烴層、(25)層(Y)/聚烯烴層/聚烯烴層、(26)層(Y)/聚烯烴層/層(Y)/聚烯烴層、(27)聚烯烴層/層(Y)/聚烯烴層、(28)層(Y)/聚酯層/聚烯烴層、(29)層(Y)/聚酯層/層(Y)/聚烯烴層、(30)聚酯層/層(Y)/聚烯烴層、(31)層(Y)/聚醯胺層/聚烯烴層、(32)層(Y)/聚醯胺層/層(Y)/聚烯烴層、(33)聚醯胺層/層(Y)/聚烯烴層、(34)層(Y)/聚酯層/紙層、(35)層(Y)/聚醯胺層/紙層、(36)層(Y)/聚烯烴層/紙層、(37)聚烯烴層/紙層/聚烯烴層/層(Y)/聚酯層/聚烯烴層、 (38)聚烯烴層/紙層/聚烯烴層/層(Y)/聚醯胺層/聚烯烴層、(39)聚烯烴層/紙層/聚烯烴層/層(Y)/聚烯烴層、(40)紙層/聚烯烴層/層(Y)/聚酯層/聚烯烴層、(41)聚烯烴層/紙層/層(Y)/聚烯烴層、(42)紙層/層(Y)/聚酯層/聚烯烴層、(43)紙層/層(Y)/聚烯烴層、(44)層(Y)/紙層/聚烯烴層、(45)層(Y)/聚酯層/紙層/聚烯烴層、(46)聚烯烴層/紙層/聚烯烴層/層(Y)/聚烯烴層/含羥基之聚合物層、(47)聚烯烴層/紙層/聚烯烴層/層(Y)/聚烯烴層/聚醯胺層、(48)聚烯烴層/紙層/聚烯烴層/層(Y)/聚烯烴層/聚酯層、(49)無機蒸鍍層/層(Y)/聚酯層、(50)無機蒸鍍層/層(Y)/聚酯層/層(Y)/無機蒸鍍層、(51)無機蒸鍍層/層(Y)/聚醯胺層、(52)無機蒸鍍層/層(Y)/聚醯胺層/層(Y)/無機蒸鍍層、(53)無機蒸鍍層/層(Y)/聚烯烴層、(54)無機蒸鍍層/層(Y)/聚烯烴層/層(Y)/無機蒸鍍層 (1) layer (Y)/polyester layer, (2) layer (Y)/polyester layer/layer (Y), (3) layer (Y)/polyamide layer, (4) layer (Y)/ Polyamide layer/layer (Y), (5) layer (Y)/polyolefin layer, (6) layer (Y)/polyolefin layer/layer (Y), (7) layer (Y)/hydroxy-containing Polymer layer, (8) layer (Y)/hydroxyl-containing polymer layer/layer (Y), (9) layer (Y)/paper layer, (10) layer (Y)/paper layer/layer (Y) , (11) layer (Y)/inorganic vapor deposited layer/polyester layer, (12) layer (Y)/inorganic vapor deposited layer/polyamide layer, (13) layer (Y)/inorganic vapor deposited layer/polyolefin layer, (14) layer (Y)/inorganic vapor deposition layer/hydroxyl-containing polymer layer, (15) layer (Y)/polyester layer/polyamide layer/polyolefin layer, (16) layer (Y)/polyester layer/layer (Y)/polyamide layer/polyolefin layer, (17) polyester layer/layer (Y)/polyester layer/layer (Y)/inorganic vapor-deposited layer /Hydroxyl-containing polymer layer/polyolefin layer, (18) polyester layer/layer (Y)/polyamide layer/polyolefin layer, (19) layer (Y)/polyamide layer/polyester layer/ Polyolefin layer, (20) layer (Y)/polyamide layer/layer (Y)/polyester layer/polyolefin layer, (21) polyamide layer/layer (Y)/polyester layer/polyolefin layer , (22) layer (Y)/polyolefin layer/polyamide layer/polyolefin layer, (23) layer (Y)/polyolefin layer/layer (Y)/polyamide layer/polyolefin layer, (24 ) Polyolefin layer/layer (Y)/polyamide layer/polyolefin layer, (25) layer (Y)/polyolefin layer/polyolefin layer, (26) layer (Y)/polyolefin layer/layer (Y )/Polyolefin layer, (27) polyolefin layer/layer (Y)/polyolefin layer, (28) layer (Y)/polyester layer/polyolefin layer, (29) layer (Y)/polyester layer/ Layer (Y)/polyolefin layer, (30) polyester layer/layer (Y)/polyolefin layer, (31) layer (Y)/polyamide layer/polyolefin layer, (32) layer (Y)/ Polyamide layer/layer (Y)/polyolefin layer, (33) Polyamide layer/layer (Y)/polyolefin layer, (34) layer (Y)/polyester layer/paper layer, (35) layer (Y)/polyamide layer/paper layer, (36) layer (Y)/polyolefin layer/paper layer, (37) polyolefin layer/paper layer/polyolefin layer/layer (Y)/polyester layer/ Polyolefin layer, (38) Polyolefin layer/paper layer/polyolefin layer/layer (Y)/polyamide layer/polyolefin layer, (39) polyolefin layer/paper layer/polyolefin layer/layer (Y)/polyolefin layer , (40) paper layer/polyolefin layer/layer (Y)/polyester layer/polyolefin layer, (41) polyolefin layer/paper layer/layer (Y)/polyolefin layer, (42) paper layer/layer (Y)/polyester layer/polyolefin layer, (43) paper layer/layer (Y)/polyolefin layer, (44) layer (Y)/paper layer/polyolefin layer, (45) layer (Y)/ Polyester layer/paper layer/polyolefin layer, (46) polyolefin layer/paper layer/polyolefin layer/layer (Y)/polyolefin layer/hydroxyl-containing polymer layer, (47) polyolefin layer/paper layer /Polyolefin layer/layer (Y)/polyolefin layer/polyamide layer, (48) polyolefin layer/paper layer/polyolefin layer/layer (Y)/polyolefin layer/polyester layer, (49) inorganic Vapor deposition layer/layer (Y)/polyester layer, (50) inorganic vapor deposition layer/layer (Y)/polyester layer/layer (Y)/inorganic vapor deposition layer, (51) inorganic vapor deposition layer/layer (Y)/poly Amine layer, (52) inorganic vapor deposition layer/layer (Y)/polyamide layer/layer (Y)/inorganic vapor deposition layer, (53) inorganic vapor deposition layer/layer (Y)/polyolefin layer, (54) inorganic Vapor deposited layer/layer (Y)/polyolefin layer/layer (Y)/inorganic vapor deposited layer
本發明之保護薄片,於上述構成中,又以(1)~(8)、(11)~(33),及(49)~(54)之任一之構成為佳。 The protective sheet of the present invention is preferably one of (1) to (8), (11) to (33), and (49) to (54) in the above configuration.
本發明之多層結構體,於殺菌處理前及殺菌處理後,20℃、85% RH之條件下的氧透過度為2.0mL/(m2.day.atm)以下,又以0.5mL/(m2.day.atm)以下為佳,以0.3mL/(m2.day.atm)以下為較佳。殺菌處理之條件、氧透過度之測定方法及測定條件,係如後述實施例所記載之內容。 Before the sterilization and after the sterilization, the multilayer structure of the present invention has an oxygen permeability of 2.0 mL/(m 2 .day.atm) or less at 0.5 mL/(m 2 .day.atm) or less, preferably 0.3mL/(m 2 .day.atm) or less. The conditions of the sterilization treatment, the measurement method and the measurement conditions of the oxygen permeability are as described in the examples described later.
本發明之多層結構體,於殺菌處理前及殺菌處理後,40℃、90% RH之條件下的透濕度以0.5g/(m2.day)以下為佳,以0.3g/(m2.day)以下為較佳。殺菌處理之條件、透濕度之測定方法及測定條件,係如後述實施例所記載之內容。 The multilayer structure of the present invention, before and after sterilization treatment, the moisture permeability under the conditions of 40°C and 90% RH is preferably 0.5 g/(m 2 .day) or less, and 0.3 g/(m 2 . day) The following is preferred. The conditions of the sterilization treatment, the measurement method and the measurement conditions of the moisture permeability are as described in the examples described later.
又,本發明之多層結構體中,殺菌處理後之層(Y)與接著層(I)或其他之層(J)(例如,油墨層)的剝離強度以超過100g/15mm者為佳,以超過110g/15mm以上者為較佳。殺菌處理之條件、剝離強度之測定方法及測定條件,係如後述實施例所記載之內容。 Furthermore, in the multilayer structure of the present invention, the peel strength of the layer (Y) and the adhesive layer (I) or other layer (J) (for example, ink layer) after sterilization treatment is preferably more than 100g/15mm, Those exceeding 110g/15mm or more are preferred. The conditions of the sterilization treatment, the measurement method and the measurement conditions of the peel strength are as described in the examples described later.
本發明之多層結構體及保護薄片,於溫濕試驗前及溫濕試驗後中,於20℃、85% RH之條件下的氧透過度為2.0mL/(m2.day.atm)以下,又以0.5mL/(m2.day.atm)以下為佳,以0.3mL/(m2.day.atm)以下為較佳。溫濕試驗之條件、氧透過度之測定方法及測定條件,係如後述實施例所記載之內容。 The multilayer structure and protective sheet of the present invention have an oxygen permeability of 2.0 mL/(m 2 .day.atm) or less under the conditions of 20° C. and 85% RH before and after the temperature and humidity test. It is preferably 0.5 mL/(m 2 .day.atm) or less, and preferably 0.3 mL/(m 2 .day.atm) or less. The conditions of the temperature and humidity test, the measurement method and the measurement conditions of the oxygen permeability are as described in the examples described later.
本發明之多層結構體及保護薄片,於溫濕試驗前及溫濕試驗後中,於40℃、90% RH之條件下的透濕 度以0.5g/(m2.day)以下為佳,以0.3g/(m2.day)以下為較佳。溫濕試驗之條件、透濕度之測定方法及測定條件,係如後述實施例所記載之內容。 The multilayer structure and the protective sheet of the present invention preferably have a permeability of 0.5 g/(m 2 .day) or less under the conditions of 40° C. and 90% RH before and after the temperature and humidity test. 0.3g/(m 2 .day) or less is preferable. The conditions of the temperature and humidity test, the measurement method and the measurement conditions of the moisture permeability are as described in the examples described later.
又,本發明之多層結構體及保護薄片,其於溫濕試驗後之層(Y)與接著層(I)或其他之層(J)(例如,油墨層)的剝離強度以超過170g/15mm者為佳,以200g/15mm以上者為較佳,以260g/15mm以上者為更佳。溫濕試驗之條件、剝離強度之測定方法及測定條件,係如後述實施例所記載之內容。 In addition, the multilayer structure and protective sheet of the present invention have a peel strength of the layer (Y) and the adhesive layer (I) or other layers (J) (for example, ink layer) after a temperature and humidity test exceeding 170 g/15 mm Whichever is better, more preferably 200g/15mm or more, more preferably 260g/15mm or more. The conditions of the temperature and humidity test, the measurement method and the measurement conditions of the peel strength are as described in the examples described later.
本發明之多層結構體及使用其之包裝材料,於具有優良氣體阻隔性及水蒸氣阻隔性的同時,即使於殺菌處理後亦具有優良氣體阻隔性及水蒸氣阻隔性,不會產生剝離等外觀不良現象、具有高層間接著力(剝離強度)。因此,本發明之多層結構體及使用其之包裝材料,可適用於各種之用途。 The multilayer structure of the present invention and the packaging material using the same have excellent gas barrier properties and water vapor barrier properties, and even after sterilization treatment, they also have excellent gas barrier properties and water vapor barrier properties without peeling and other appearances Defective phenomenon, with adhesion between high layers (peel strength). Therefore, the multilayer structure of the present invention and the packaging material using the same can be applied to various uses.
本發明之包裝材料為含有含基材(X),與層合於基材(X)上之層(Y)的多層結構體。包裝材料,可僅由多層結構體所構成。即,以下之說明中,「包裝材料」亦可稱為「多層結構體」。又,典型而言,「包裝材料」可以稱為「包裝」。包裝材料,亦可由多層結構體與其他構件所構 成。 The packaging material of the present invention is a multilayer structure including a base material (X) and a layer (Y) laminated on the base material (X). The packaging material may be composed of only a multilayer structure. That is, in the following description, "packaging material" may also be referred to as "multilayer structure". Also, typically, "packaging materials" can be called "packaging." Packaging materials can also be constructed from multilayer structures and other components to make.
本發明之較佳實施形態之包裝材料,對於無機氣體(例如,氫、氦、氮、氧、二氧化碳)、天然氣體、水蒸氣及常溫常壓為液體狀的有機化合物(例如,乙醇、石油氣)具有阻隔性。 The packaging material of the preferred embodiment of the present invention is suitable for inorganic gases (for example, hydrogen, helium, nitrogen, oxygen, carbon dioxide), natural gas, water vapor, and organic compounds that are liquid at normal temperature and pressure (for example, ethanol, petroleum gas) ) Has barrier properties.
本發明之包裝材料為包裝袋之情形,該包裝袋的全部可使用多層結構體而構成,或其包裝袋之一部份使用多層結構體者亦可。例如,包裝袋的面積之50%~100%,可由多層結構體所構成者亦可。包裝材料為包裝袋以外者(例如,容器、蓋材)之情形亦為相同。 In the case where the packaging material of the present invention is a packaging bag, all of the packaging bag may be formed using a multilayer structure, or a part of its packaging bag may use a multilayer structure. For example, 50% to 100% of the area of the packaging bag may be composed of a multilayer structure. The same applies when the packaging material is other than a packaging bag (for example, a container or a lid material).
本發明之包裝材料,可使用各種方法予以製得。例如,可將薄片狀之多層結構體或含有該多層結構體之薄膜材料(以下,亦僅稱為「薄膜材料」)接合,並依特定之容器形狀予以成形,而製得容器(包裝材料)亦可。成形方法,例如,熱成形、射出成形、擠壓流動成形等。又,經於成形於特定容器之形狀的基材(X)之上形成層(Y)之方式,而製得容器(包裝材料)亦可。使用該些方法所製得之容器,於本說明書中,亦稱為「包裝容器」。 The packaging material of the present invention can be prepared using various methods. For example, a sheet-like multilayer structure or a film material containing the multilayer structure (hereinafter, also simply referred to as "film material") can be joined and shaped according to a specific container shape to produce a container (packaging material) Also. Molding methods, for example, thermoforming, injection molding, extrusion flow molding, etc. Furthermore, a container (packaging material) may be produced by forming a layer (Y) on a base material (X) shaped into a specific container shape. The containers made by these methods are also called "packaging containers" in this specification.
本發明之包裝材料,適合作為食品用包裝材料使用。又,本發明之包裝材料,除適合作為食品用包裝材料以外,亦適合作為包裝農藥、醫藥等藥品;醫療器材;機械零件、精密材料等產業資材;衣料等所使用之包裝材料。 The packaging material of the present invention is suitable for use as a packaging material for food. In addition, the packaging material of the present invention is not only suitable as a packaging material for food, but also suitable for packaging pesticides, medicines and other pharmaceuticals; medical equipment; mechanical parts, precision materials and other industrial materials; clothing materials and other packaging materials used.
又,含有本發明之多層結構體的包裝材料, 可使用二次加工製得各種成形品。該些成形品,可為縱製袋填充密封袋、真空包裝袋、袋(pouch)、層合管狀容器、輸注液袋(bag)、紙容器、長條袋、容器用蓋材、模內標籤(In Mold Labeling)容器、真空隔熱體,或電子裝置。該些成形品,亦可進行熱密封處理。 Moreover, the packaging material containing the multilayer structure of the present invention, Various molded products can be produced using secondary processing. These molded products can be vertical bag filled sealed bags, vacuum packaging bags, pouches, laminated tubular containers, infusion solution bags (bags), paper containers, long bags, lid materials for containers, in-mold labels (In Mold Labeling) containers, vacuum insulation, or electronic devices. These molded products can also be heat-sealed.
含有本發明之多層結構體之包裝材料,可為縱製袋填充密封袋。其例如圖1所示。圖1所示之縱製袋填充密封袋10,為將本發明之多層結構體11,以2個端部11a與本體部11b以三方密封方式而形成者。縱製袋填充密封袋10可使用縱型製袋填充機予以製造。使用縱型製袋填充機製袋之方法,可使用各種方法進行,但任一方法中,皆為使內容物為袋之上方開口供應於內部,隨後將該開口密封而製得縱製袋填充密封袋。縱製袋填充密封袋,例如,上端、下端,及側部等三方中,皆可由熱密封之1片的薄膜材料所構成。本發明之作為包裝容器之縱製袋填充密封袋,因具有優良氣體阻隔性及水蒸氣阻隔性,且殺菌處理後亦可維持阻隔性能,故該縱製袋填充密封袋,可長期間抑制內容物之品質劣化。
The packaging material containing the multi-layer structure of the present invention can be a vertical bag filled and sealed bag. This is shown in Figure 1, for example. The vertical bag-filled and sealed
含有本發明之多層結構體的包裝材料可為袋(pouch)。其例如圖2所示。圖2之平袋(flat pouch)20,為由2片之
多層結構體11,由其周邊部11c互相接合方式予以形成。本說明書中,「袋」之用語,主要為以食品、日用品或醫藥品作為內容物之具有由薄膜材料作為壁構件的容器之意。袋(pouch),例如,依其形狀及用途,可區分為,壺口袋(spout pouch)、夾鏈袋、平袋(flat pouch)、立袋(stand up pouch)、橫製袋填充密封袋、殺菌袋(retort pouch)等。袋,可由多層結構體,與至少1層之其他之層(J)經層合而形成。本發明之作為包裝容器之袋,具有優良氣體阻隔性及水蒸氣阻隔性,即使殺菌處理後亦可維持其阻隔性能。因此,使用該袋時,即使於輸送後或長期保存後,亦可防止內容物之變質。又,該袋之例示中,因可保持良好之透明性,故容易進行內容物之確認、確認因劣化所造成之內容物的變質情形。
The packaging material containing the multilayer structure of the present invention may be a pouch. This is shown in Figure 2 for example. Figure 2 flat pouch (flat pouch) 20, is composed of 2 pieces
The
包含本發明之多層結構體的包裝材料,可為輸注液袋。輸注液袋為,以液體製劑為其內容物之容器,其具備有區隔存放輸注液製劑之內部與外部而作為隔壁之薄膜材料。其例如圖3所示。如圖3所示般,輸注液袋(bag),除存放內容物之輸注液袋本體431以外,於輸注液袋本體431之周邊部412亦可具備有口栓構件432。口栓構件432,具有作為將存放於輸注液袋本體431內部的輸注液類取出之通路的機能。又,輸注液袋上,就使輸注液袋得以吊掛之目的,於裝設有口栓構件432之周邊部412的相
對側之周邊部411可設置吊掛孔433。輸注液袋本體431,為由2片之薄膜材料410a、410b於其之周邊部411、412、413、414上互相接合之方式予以形成。薄膜材料410a、410b,於輸注液袋本體431之周邊部411、412、413、414所包圍之中央部中,作為區隔輸注液袋內部與輸注液袋外部之隔壁420的機能。本發明之作為包裝容器之輸注液袋,具有優良之氣體阻隔性,經熱水處理等殺菌處理後仍可維持其氣體阻隔性。因此,該輸注液袋,即使於加熱殺菌處理前、加熱殺菌處理中、加熱殺菌處理後、輸送後、保存後,皆可防止所填充之液狀醫藥品產生變質。
The packaging material containing the multilayer structure of the present invention may be an infusion solution bag. The infusion solution bag is a container with a liquid preparation as its content, and it is provided with a film material that separates the inside and the outside of the infusion solution preparation as a partition wall. This is shown in Figure 3, for example. As shown in FIG. 3, in addition to the
包含本發明之多層結構體的包裝材料,可為模內標籤容器。模內標籤容器,為包含容器本體,與配置於容器本體表面之本發明之多層標籤(多層結構體)。容器本體,為經由將熔融樹脂注入模型內部之方式而形成。容器本體之形狀並未有特別之限定,可為杯狀、瓶狀等。 The packaging material containing the multilayer structure of the present invention may be an in-mold label container. The in-mold label container includes the container body and the multilayer label (multilayer structure) of the present invention disposed on the surface of the container body. The container body is formed by injecting molten resin into the mold. The shape of the container body is not particularly limited, and may be cup-shaped, bottle-shaped, and the like.
本發明中製造容器之方法之一例為,包含於母模型部與公模型部之間的模槽內配置本發明之多層標籤之第1步驟,與於該模槽內注入熔融樹脂之方式,同時進行容器本體之成形與將本發明之多層標籤貼付於該容器本體之第2步驟。除使用本發明之多層標籤以外,各步驟皆可使用公知之方法予以實施。 An example of the method of manufacturing a container in the present invention is that the first step of arranging the multilayer label of the present invention in the cavity between the female model part and the male model part, and the method of pouring molten resin into the cavity, simultaneously The second step of forming the container body and applying the multilayer label of the present invention to the container body. Except for the use of the multilayer label of the present invention, each step can be implemented using a well-known method.
本發明之容器之一例示的截面圖係如圖4所示。容器360,為包含杯狀之容器本體370,與貼付於容器本體370表面之多層標籤361~363。多層標籤361~363為本發明之多層標籤。容器本體370,為包含凸緣部371與本體部372與底部373。凸緣部371,於其前端,具有上下突出之凸部371a。多層標籤361,為以被覆底部373之外側表面之方式配置。多層標籤361之中央,形成有於模內標籤成形時,注入樹脂所使用之貫通孔361a。多層標籤362,為以被覆本體部372之外側表面與凸緣部371之下面之方式配置。多層標籤363,為以被覆本體部372之內側表面的一部份與凸緣部371之上面之方式配置。多層標籤361~363,經由模內標籤成形法,而融著於容器本體370,與容器本體360形成一體。如圖4所示般,多層標籤363之端面,為融著於容器本體360,未露出於外部。
An exemplary cross-sectional view of one container of the present invention is shown in FIG. 4. The
將前述包裝材料作為至少一部份使用的本發明之製品,可為真空隔熱體。真空隔熱體為具備,被覆材料,與被覆材料所包圍之配置於內部的芯材之隔熱體,芯材所配置之內部為減壓之狀態。真空隔熱體可以更輕薄之隔熱體達成與聚胺基甲酸酯發泡體所形成之隔熱體所具有隔熱特性為同等的隔熱特性。本發明之真空隔熱體,可被利用作為冰箱、熱水器及電鍋等家電製品用之隔熱材料;牆壁、 天花板、屋簷內部及地板等所使用之住宅用隔熱材、車輛頂棚材料、自動販賣機等之隔熱板;蓄熱機器、加熱幫浦應用機器等熱移動機器等。作為被覆材料使用之本發明之多層結構體,亦可含有乙烯-乙烯醇共聚物樹脂層及無機蒸鍍層,例如,可具有聚酯層/層(Y)/聚酯層/層(Y)/無機蒸鍍層/乙烯-乙烯醇共聚物層/聚烯烴層之構成。 The product of the present invention using the aforementioned packaging material as at least a part may be a vacuum heat insulator. The vacuum insulation body is a heat insulation body provided with a coating material and a core material arranged inside surrounded by the coating material, and the inside of the core material is arranged in a reduced pressure state. The vacuum insulation body can achieve a heat insulation property equal to that of the heat insulation body formed of the polyurethane foam with a lighter and thinner heat insulation body. The vacuum insulation body of the present invention can be used as a heat insulation material for household appliances such as refrigerators, water heaters and electric pots; walls, Insulation materials for residential use, vehicle roof materials, heat insulation boards for vending machines, etc. used in ceilings, eaves interiors, floors, etc.; heat moving equipment such as heat storage equipment, heating pump application equipment, etc. The multilayer structure of the present invention used as a coating material may also contain an ethylene-vinyl alcohol copolymer resin layer and an inorganic vapor deposition layer, for example, may have a polyester layer/layer (Y)/polyester layer/layer (Y)/ Composition of inorganic vapor deposition layer/ethylene-vinyl alcohol copolymer layer/polyolefin layer.
本發明之真空隔熱體之一例示如圖6所示。圖6之真空隔熱體601,為含有粒子狀之芯材651,與作為被覆其被覆材料的2片本發明之多層結構體631,632。2片之多層結構體631,632,於周邊部611中為互相接合者。由2片之多層結構體631,632所形成之內部空間,為填充芯材651,其內部空間為減壓狀態。多層結構體631,632,具有阻隔存放芯材651之內部與外部的作為隔壁之機能,其經由真空隔熱體601之內部與外部之壓力差,而密著於芯材651。芯材652所配置之內部為減壓之狀態。
An example of the vacuum heat insulator of the present invention is shown in FIG. 6. The
本發明之真空隔熱體之另一例示如圖7所示。真空隔熱體602,除芯材651以具備一體成形之芯材652替代以外,他皆具有與真空隔熱體601為相同之構成。成形體作為成形體之芯材652,典型之例示為樹脂之發泡體。
Another example of the vacuum heat insulator of the present invention is shown in FIG. 7. The
芯材之材料及形狀,只要適合作為隔熱用時,並未有特別之限制。芯材,例如,波來鐵(pearlite)粉末、二氧化矽粉末、沈降二氧化矽粉末、矽藻土、矽酸 鈣、玻璃棉、石棉、人工(合成)棉、樹脂之發泡體(例如,苯乙烯發泡體、聚胺基甲酸酯發泡體)等。芯材,可使用依特定形狀成形而得之中空容器、蜂巢結構體等。 The material and shape of the core material are not particularly limited as long as they are suitable for heat insulation. Core material, for example, pearlite powder, silica powder, precipitated silica powder, diatomaceous earth, silicic acid Calcium, glass wool, asbestos, artificial (synthetic) cotton, resin foam (for example, styrene foam, polyurethane foam), etc. For the core material, a hollow container, a honeycomb structure, etc. formed by a specific shape can be used.
包含本發明之多層結構體的包裝材料,亦可使用於電子裝置。本發明之電子裝置之一例示,其部份截面圖係如圖8所示。圖8之電子裝置40,為具備電子裝置本體41,與密封電子裝置本體41之密封材料42,與保護電子裝置本體41之表面的保護薄片(多層結構體)43。密封材料42為被覆電子裝置本體41之全體表面。保護薄片43,為於電子裝置本體41之一側的表面上,介由密封材料42予以配置。與配置有保護薄片43之表面為相反側之表面,亦可配置保護薄片43。該情形中,配置於該相反側之表面的保護薄片,與保護薄片43可為相同或相異。保護薄片43,可介由密封材料42等其他構件配置於電子裝置本體41上亦可、直接配置於電子裝置本體41之表面亦可。
The packaging material including the multilayer structure of the present invention can also be used in electronic devices. An example of an electronic device of the present invention, a partial cross-sectional view is shown in FIG. 8. The
電子裝置本體41,並未有特別之限制,例如,太陽電池等光電變換裝置;有機EL顯示器、液晶顯示器、電子紙等資訊顯示裝置;有機EL發光元件等照明裝置等。密封材料42,可配合電子裝置本體41之種類及用途等,適當地附加任意之構件。密封材料42,例如,乙烯-乙酸乙烯酯共聚物、聚乙烯縮丁醛等。
The
電子裝置本體41之較佳例示,例如,太陽電池。太陽電池,例如,矽系太陽電池、化合物半導體太陽電池、有機薄膜太陽電池等。矽系太陽電池,例如,單晶矽太陽電池、多晶矽太陽電池、非晶矽太陽電池等。化合物半導體太陽電池,例如,III-V族化合物半導體太陽電池、II-VI族化合物半導體太陽電池、I-III-VI族化合物半導體太陽電池等。又,太陽電池,可為由複數個單元晶胞直列連結而得之集積型太陽電池亦可、非集積型之太陽電池亦可。
A preferred example of the
本發明之多層結構體及含有其之包裝材料,適合使用作為LCD用基板薄膜、有機EL用基板薄膜、電子紙用基板薄膜、電子裝置用密封薄膜、PDP用薄膜等顯示器構件;IC標籤用薄膜、太陽電池模組、太陽電池用背板、太陽電池用保護薄膜等太陽電池構件。多層結構體作為顯示器之構件使用之情形,例如可作為低反射性薄膜使用。任一情形中,多層結構體需要透光性之情形時,層(Y)可使用具有透光性之層(Y)。 The multilayer structure of the present invention and the packaging material containing it are suitable for use as display members such as LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, etc.; IC label films , Solar cell module, solar cell back sheet, solar cell protective film and other solar cell components. When the multilayer structure is used as a member of a display, it can be used as a low-reflection film, for example. In any case, when the multilayer structure requires light transmission, the layer (Y) may use a layer (Y) having light transmission.
電子裝置本體41,依其種類之不同,亦可使用所謂捲對捲(Roll-to-Roll)之方式予以製得。捲對捲(Roll-to-Roll)方式中,可將捲曲於送出滾筒之可撓性之基板(例如,不銹鋼基板、樹脂基板等)送出,於該基板上形成元件之方式製作電子裝置本體41,再將此電子裝置本體41捲取於捲取滾筒。此時,保護薄片43亦可先準備為具有可撓性的長型薄片之形態,更具體而言,為準備具有
長型薄片的捲曲體之形態。舉例而言,由送出滾筒所送出之保護薄片43,層合於被捲取滾筒捲取前之電子裝置本體41上,而與電子裝置本體41共同被捲取。另一例示為,預先將捲取於捲取滾筒之電子裝置本體41而滾筒送出,再與保護薄片43層合之方式亦可。本發明之較佳例示中,電子裝置本身為具有可撓性者。
The
保護薄片43,為含有本發明之多層結構體。保護薄片43,可僅由多層結構體所構成。或,保護薄片43,可含有多層結構體,與層合於多層結構體之其他構件(例如,其他之層(J))亦可。保護薄片43,為適合作為保護電子裝置之表面的層狀之層合物,且含有前述多層結構體時,其厚度及材料並未有特別之限制。
The
保護薄片,例如,可包含配置於多層結構體之一側表面或兩側表面的表面保護層。表面保護層,以由不易受到損傷之樹脂所形成之層為佳。又,如太陽電池般,為室外所使用之裝置的表面保護層時,以由高耐候性(例如,耐光性)之樹脂所形成者為佳。又,保護必須透過光線之面的情形時,以高透光性之表面保護層為佳。表面保護層(表面保護薄膜)之材料,例如,聚(甲基)丙烯酸酯、聚碳酸酯、聚對苯二甲酸乙二酯、聚2,6-萘二甲酸乙二酯、聚氟乙烯(PVF)、聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚氯三氟乙烯(PCTFE)、乙烯-四氟乙烯共聚物(ETFE)、乙烯-氯三氟乙烯共聚物(ECTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物 (FEP)等。保護薄片之例示,為包含配置於一側表面之聚(甲基)丙烯酸酯層。 The protective sheet, for example, may include a surface protective layer disposed on one side surface or both side surfaces of the multilayer structure. The surface protection layer is preferably a layer formed of a resin that is not easily damaged. In addition, like a solar cell, when it is a surface protective layer of a device used outdoors, it is preferably formed of a resin with high weather resistance (for example, light resistance). In addition, when protecting the surface that must pass through the light, a surface protection layer with high transparency is preferred. The material of the surface protective layer (surface protective film), for example, poly(meth)acrylate, polycarbonate, polyethylene terephthalate, polyethylene 2,6-naphthalene dicarboxylate, polyvinyl fluoride ( PVF), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE) , Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) etc. An example of the protective sheet includes a poly(meth)acrylate layer disposed on one surface.
就提高表面保護層之耐久性之觀點,表面保護層可添加各種之添加劑(例如,紫外線吸收劑)。具有高耐候性之表面保護層之較佳例示,如添加有紫外線吸收劑之丙烯酸樹脂層。紫外線吸收劑,例如,苯併三唑系、二苯甲酮系、水楊酸酯系、氰基丙烯酸酯系、鎳系、三系之紫外線吸收劑等,但並不僅限定於該些內容。又,亦可併用其他之安定劑、光安定劑、抗氧化劑等。 From the viewpoint of improving the durability of the surface protective layer, various additives (for example, ultraviolet absorbers) may be added to the surface protective layer. A preferred example of a surface protective layer with high weather resistance is an acrylic resin layer added with an ultraviolet absorber. UV absorbers, for example, benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, trivalent The ultraviolet absorber, etc., but not limited to these contents. In addition, other stabilizers, light stabilizers, antioxidants, etc. may be used in combination.
以下,將列舉實施例對本發明作更具體之說明,但本發明並不受該些實施例之任何限制,於本發明之技術思想內,該領域中具有通常知識之人士皆可進行各種之改變。以下之實施例及比較例中所進行之分析及評估,係依以下方式進行。 Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these embodiments. Within the technical idea of the present invention, persons with ordinary knowledge in the field can make various changes. . The analysis and evaluation performed in the following examples and comparative examples are performed in the following manner.
使用傅力葉轉換紅外線分光光度計,依衰減全反射法予以測定。測定條件係如以下所示。 Using Fourier transform infrared spectrophotometer, it was measured according to the attenuation total reflection method. The measurement conditions are shown below.
裝置:PerkinElmer股份有限公司製Spectrum One Installation: Spectrum One manufactured by PerkinElmer Co., Ltd.
測定模式:衰減全反射法 Measurement mode: Attenuated total reflection method
測定區域:800~1,400cm-1 Measuring area: 800~1,400cm -1
使用聚焦離子束(FIB)切削多層結構體,製得截面觀察用之切片。所製得之切片使用碳膠帶固定於試料台上,以加速電壓30kV進行30秒鐘之鉑離子濺鍍。使用電場發射穿透型電子顯微鏡觀察多層結構體之截面,並算出各層之厚度。測定條件係如以下所示。 A focused ion beam (FIB) was used to cut the multilayer structure to prepare a slice for cross-sectional observation. The prepared slices were fixed on the sample table using carbon tape, and platinum ion sputtering was performed at an acceleration voltage of 30 kV for 30 seconds. Observe the cross-section of the multilayer structure using an electric field emission transmission electron microscope and calculate the thickness of each layer. The measurement conditions are shown below.
裝置:日本電子股份有限公司製JEM-2100F Device: JEM-2100F manufactured by Japan Electronics Corporation
加速電壓:200kV Acceleration voltage: 200kV
倍率:250,000倍 Magnification: 250,000 times
於氧透過量測定裝置上,以基材之層面向載體氣體側之方式裝設樣品,並以等壓法測定氧透過度。測定條件係如以下所示。 A sample is installed on the oxygen permeability measuring device with the layer of the base material facing the carrier gas side, and the oxygen permeability is measured by the isobaric method. The measurement conditions are shown below.
裝置:現代控制公司製MOCON OX-TRAN2/20 Device: MOCON OX-TRAN2/20 made by Hyundai Control Company
溫度:20℃ Temperature: 20℃
氧供應側之濕度:85% RH Humidity on the oxygen supply side: 85% RH
載體氣體側之濕度:85% RH Humidity of carrier gas side: 85% RH
氧壓:1.0atm Oxygen pressure: 1.0atm
載體氣體壓力:1.0atm Carrier gas pressure: 1.0atm
於水蒸氣透過量測定裝置上,以基材之層面向載體氣體側之方式裝設樣品,並使用等壓法測定透濕度(水蒸氣 透過度)。測定條件係如以下所示。 On the water vapor transmission rate measuring device, install the sample with the layer of the base material facing the carrier gas side, and use the isobaric method to measure the moisture permeability (water vapor Transmittance). The measurement conditions are shown below.
裝置:現代控制公司製MOCON PERMATRAN W3/33 Device: MOCON PERMATRAN W3/33 made by Hyundai Control Corporation
溫度:40℃ Temperature: 40℃
水蒸氣供應側之濕度:90% RH Humidity on the water vapor supply side: 90% RH
載體氣體側之濕度:0% RH Humidity of carrier gas side: 0% RH
使用T型剝離強度測定(每一寬15mm時之接著力)評估密著性。進行5次測定,採其平均值。測定條件係如以下所示。 The adhesion was evaluated using a T-shaped peel strength measurement (adhesion force at each 15 mm width). Five measurements were made and the average value was taken. The measurement conditions are shown below.
裝置:島津製作所股份有限公司製高壓釜AGS-H Device: Autoclave AGS-H manufactured by Shimadzu Corporation
剝離速度:250mm/分鐘 Peeling speed: 250mm/min
溫度:23℃ Temperature: 23℃
濕度:50% RH Humidity: 50% RH
將蒸餾水230質量份於攪拌中升溫至70℃。將三異丙氧基鋁88質量份以1小時滴入該蒸餾水中,使液溫緩緩上升至95℃為止,將所產生之異丙醇餾出以進行水解縮合。於所得液體中,添加60質量%之硝酸水溶液4.0質量份,於95℃下攪拌3小時使水解縮合物之粒子凝聚物解膠。隨後,將該液體濃縮至固形分濃度以氧化鋁換算為10質量%為止,而製得溶液。對依此方式所得之溶液 22.50質量份,加入蒸餾水54.29質量份及甲醇18.80質量份,將其攪拌至均勻而製得分散液。隨後,將液溫維持於15℃狀態,於持續攪拌分散液中,以滴入方式加入85質量%之磷酸水溶液4.41質量份,於15℃下持續攪拌至黏度達1,500mPa.s為止,而得目的之塗覆液(S-1)。該塗覆液(S-1)中,鋁原子與磷原子之莫耳比為,鋁原子:磷原子=1.15:1.00。 230 mass parts of distilled water was heated to 70 degreeC with stirring. 88 parts by mass of aluminum triisopropoxide was dropped into this distilled water over 1 hour, the liquid temperature was gradually raised to 95°C, and the produced isopropanol was distilled off for hydrolysis and condensation. To the obtained liquid, 4.0 parts by mass of a 60% by mass nitric acid aqueous solution was added, and the mixture was stirred at 95° C. for 3 hours to degel the particle condensate of the hydrolyzed condensate. Subsequently, the liquid was concentrated to a solid concentration of 10% by mass in terms of alumina, and a solution was prepared. For the solution obtained in this way 22.50 parts by mass, 54.29 parts by mass of distilled water and 18.80 parts by mass of methanol were added, and the mixture was stirred to make a dispersion. Subsequently, the liquid temperature was maintained at 15 ℃ state, in the continuous stirring dispersion, 84.1 mass parts of phosphoric acid aqueous solution of 4.41 parts by mass was added dropwise, and stirring was continued at 15 ℃ until the viscosity reached 1,500 mPa. s, the desired coating solution (S-1). In this coating solution (S-1), the molar ratio of aluminum atoms to phosphorus atoms is aluminum atoms: phosphorus atoms = 1.15: 1.00.
於氮氛圍下,將甲基丙烯酸2-膦醯氧乙酯8.5g及偶氮雙異丁腈0.1g溶解於甲基乙基酮17g中,於80℃下攪拌12小時。冷卻後,將所得聚合溶液加入1,2-二氯乙烷170g中,經由傾析處理,以沈澱物方式回收目的之聚合物。隨後,將聚合物溶解於四氫呋喃,將1,2-二氯乙烷作為貧溶劑使用,進行再沈澱精製。經進行3次再沈澱精製後,於50℃下進行24小時真空乾燥,得目的之PPEM。經GPC分析結果,該聚合物之數平均分子量以聚苯乙烯換算為2,950。 Under a nitrogen atmosphere, 8.5 g of 2-phosphonooxyethyl methacrylate and 0.1 g of azobisisobutyronitrile were dissolved in 17 g of methyl ethyl ketone and stirred at 80° C. for 12 hours. After cooling, the resulting polymerization solution was added to 170 g of 1,2-dichloroethane, and the target polymer was recovered as a precipitate through decantation treatment. Subsequently, the polymer was dissolved in tetrahydrofuran, 1,2-dichloroethane was used as a lean solvent, and reprecipitation purification was performed. After reprecipitation purification three times, vacuum drying was performed at 50°C for 24 hours to obtain the desired PPEM. According to GPC analysis results, the number average molecular weight of the polymer is 2,950 in terms of polystyrene.
於氮氛圍下,將乙烯膦酸10g及2,2’-偶氮雙(2-甲脒基丙烷)2鹽酸鹽0.025g溶解於水5g中,於80℃下攪拌3小時。冷卻後,於聚合溶液中加入水15g進行稀釋,使用纖維素膜之Spectrum Laboratories公司製<Spectra/ Por(登記商標)>進行過濾。餾除濾液中之水份之後,於50℃下進行24小時真空乾燥,得目的之PVPA。經GPC分析結果,該聚合物之數平均分子量以聚乙二醇換算為10,800。 Under a nitrogen atmosphere, 10 g of ethylenephosphonic acid and 0.025 g of 2,2'-azobis(2-carboxamidopropane) 2 hydrochloride were dissolved in 5 g of water, and stirred at 80°C for 3 hours. After cooling, 15 g of water was added to the polymerization solution for dilution, and the cellulose membrane was used by Spectrum Laboratories <Spectra/ Por (registered trademark)> filter. After distilling off the water in the filtrate, vacuum drying was carried out at 50°C for 24 hours to obtain the desired PVPA. According to GPC analysis results, the number average molecular weight of the polymer is 10,800 in terms of polyethylene glycol.
使磷酸酯化率RBP=0.67之方式,將85質量%磷酸水溶液0.71質量份與5質量%聚乙烯醇(KURARAY股份有限公司製「KURARAY-POVAL(登記商標)PVA124」;皂化度98.5莫耳%、黏度平均聚合度2,400、20℃之4質量%水溶液黏度60mPa.s)水溶液8.0質量份混合,於25℃下攪拌1小時。隨後,使用旋轉蒸發器由所得混合液中餾除水份,於40℃下進行12時間減壓處理後,得乾固物。使用熱風乾燥機對該乾固物進行120℃、3分鐘加熱處理,得目的物之磷酸酯化物(BP-1)白色固體。經測定磷酸酯化物(BP-1)之紅外線吸收圖譜結果,確認於1,250~1,300cm-1上具有磷酸酯之P=O伸縮振動之特定的吸收。 Using a phosphoric acid esterification rate R BP =0.67, 0.71 parts by mass of 85% by mass phosphoric acid aqueous solution and 5% by mass of polyvinyl alcohol ("KURARAY-POVAL (registered trademark) PVA124" manufactured by KURARAY Co., Ltd.; saponification degree 98.5 mol) %, viscosity average polymerization degree 2,400, 4 mass% aqueous solution viscosity at 20°C 60mPa.s) 8.0 parts by mass of aqueous solution were mixed, and stirred at 25°C for 1 hour. Subsequently, water was distilled off from the obtained mixed liquid using a rotary evaporator, and the depressurization treatment was carried out at 40°C for 12 hours to obtain a dry solid. This dry solid substance was subjected to a heat treatment at 120°C for 3 minutes using a hot air dryer to obtain a phosphoric acid ester (BP-1) white solid of the target substance. By measuring the infrared absorption spectrum of the phosphate ester (BP-1), it was confirmed that there was a specific absorption of the P=O stretching vibration of the phosphate ester at 1,250 to 1,300 cm -1 .
將磷酸酯化物(BP-1)溶解於水69.30質量份與甲醇29.70質量份之混合溶劑,得固形分濃度為1.0質量%之塗覆液(T-1)。 The phosphate ester (BP-1) was dissolved in a mixed solvent of 69.30 parts by mass of water and 29.70 parts by mass of methanol to obtain a coating solution (T-1) with a solid content concentration of 1.0% by mass.
將85質量%磷酸水溶液0.71質量份及5質量%聚乙烯醇(KURARAY股份有限公司製「KURARAY-POVAL(登記商標)PVA124」;皂化度98.5莫耳%、黏度平均聚合度2,400、20℃下之4質量%水溶液黏度60mPa.s)水溶液8.0質量份,溶解於水61.59質量份與甲醇29.70質量份之混合溶劑中,得固形分濃度為1.0質量%之塗覆液(T-2)。 0.71 parts by mass of 85% by mass phosphoric acid aqueous solution and 5% by mass of polyvinyl alcohol ("KURARAY-POVAL (registered trademark) PVA124" manufactured by KURARAY Co., Ltd.; saponification degree 98.5 mol%, average viscosity polymerization degree 2,400, at 20 ℃ 4% by mass aqueous solution viscosity 60mPa.s) 8.0 parts by mass of aqueous solution, dissolved in a mixed solvent of 61.59 parts by mass of water and 29.70 parts by mass of methanol to obtain a coating solution (T-2) with a solid concentration of 1.0% by mass.
實施例及比較例所使用之薄膜的詳細內容係如以下所示。 The details of the films used in Examples and Comparative Examples are shown below.
1)PET12:延伸聚對苯二甲酸乙酯薄膜;東麗股份有限公司製、「LUMIRROR P60」(商品名)、厚度12μm 1) PET12: Stretched polyethylene terephthalate film; "LUMIRROR P60" (trade name) manufactured by Toray Industries, Ltd., thickness 12 μm
2)PET50:提高與乙烯-乙酸乙烯酯共聚物之接著性的聚對苯二甲酸乙二酯薄膜;東洋紡股份有限公司製、「SHINEBEAN Q1A15」(商品名)、厚度50μm
2) PET50: polyethylene terephthalate film with improved adhesion to ethylene-vinyl acetate copolymer; manufactured by Toyobo Co., Ltd., "SHINEBEAN Q1A15" (trade name),
3)ONY:延伸尼龍薄膜;UNITIKA股份有限公司製、「EMBLEM ONBC」(商品名)、厚度15μm 3) ONY: stretch nylon film; "EMBLEM ONBC" (trade name) manufactured by UNITIKA Corporation, 15 μm thick
4)CPP60:無延伸聚丙烯薄膜;三井化學TOHCELLO股份有限公司製、「RXC-21」(商品名)、厚度60μm 4) CPP60: non-stretched polypropylene film; made by Mitsui Chemicals TOHCELLO Co., Ltd., "RXC-21" (trade name), thickness 60 μm
5)CPP70:無延伸聚丙烯薄膜;三井化學TOHCELLO股份有限公司製、「RXC-21」(商品名)、厚度70μm 5) CPP70: non-stretched polypropylene film; made by Mitsui Chemicals TOHCELLO Co., Ltd., "RXC-21" (trade name), thickness 70 μm
6)CPP100:無延伸聚丙烯薄膜;三井化學TOHCELLO股份有限公司製、「RXC-21」(商品名)、厚度100μm 6) CPP100: non-stretched polypropylene film; made by Mitsui Chemicals TOHCELLO Co., Ltd., "RXC-21" (trade name), thickness 100 μm
首先,準備作為基材(X)之PET12(以下,亦簡稱為「X-1」)。於此基材上,使用棒狀塗佈機以乾燥後之厚度達0.3μm之方式塗佈塗覆液(S-1)。塗佈後之薄膜,經由於110℃、5分鐘乾燥後之後,再經160℃、1分鐘熱處理結果,於基材上形成層(Y-1-1)之前驅體。此外,使用棒狀塗佈機使磷酸酯化物(BP)之塗佈量達30mg/m2之方式,塗佈塗覆液(S-1),於110℃下進行3分鐘乾燥。隨後,進行220℃、1分鐘之熱處理,而形成層(Y-1-1)。依此方式,而製得具有基材(X-1)/層(Y-1-1)之構造的多層結構體(1-1-1)。 First, PET12 (hereinafter, also simply referred to as "X-1") as a base material (X) is prepared. On this substrate, a bar coater was used to apply the coating liquid (S-1) so that the thickness after drying was 0.3 μm. After the coated film was dried at 110°C for 5 minutes, the film was heat-treated at 160°C for 1 minute, and a precursor (Y-1-1) was formed on the substrate. In addition, the coating liquid (S-1) was applied so that the coating amount of phosphate ester (BP) reached 30 mg/m 2 using a bar coater, and dried at 110° C. for 3 minutes. Subsequently, heat treatment at 220°C for 1 minute was performed to form a layer (Y-1-1). In this way, a multilayer structure (1-1-1) having a structure of base material (X-1)/layer (Y-1-1) was produced.
經測定多層結構體(1-1-1)之紅外線吸收圖譜結果,得知800~1,400cm-1之區域中的最大吸收波數以1,108cm-1,該最大吸收帶之半高寬值(FWHM)為37cm-1。 By measuring the infrared absorption spectrum of the multilayer structure (1-1-1), it is found that the maximum absorption wavenumber in the region of 800~1,400 cm -1 is 1,108 cm -1 , and the half-height width of the maximum absorption band is ( FWHM) is 37 cm -1 .
於所得多層結構體(1-1-1)上形成油墨層,於40℃下靜置1日進行蝕刻。隨後形成接著層,於該接著層上層合ONY而製得層合物。其次,於該層合物之ONY上形成接著層之後,於該接著層上,層合CPP70,於40℃下靜置5日進行蝕刻。依此方式,即可形成具有基材(X-1)/層(Y-1-1)/油墨層/接著層/ONY/接著層/CPP之構造的多層結構體(1-1-2)。使用棒狀塗佈機,將上述2個接著層分別以乾燥後之厚度達3μm之方式,塗佈2液型接 著劑,經乾燥後而形成。2液型接著劑為使用三井化學股份有限公司製之「TAKALAKE」(登記商標)之「A-525S」(商標)與三井化學股份有限公司製之「TAKANATE」(登記商標)之「A-50」(商標)與所形成之2液反應型聚胺基甲酸酯系接著劑。又,前述油墨層為,使用棒狀塗佈機以乾燥後之厚度為2μm之方式進行塗佈,經乾燥後而形成者。油墨為使用東洋油墨股份有限公司製之「FINESTAR」(登記商標)之「R641AT白」(商標)與東洋油墨股份有限公司製「LP超級硬化劑」(商標)與所形成之油墨。測定多層結構體(1-1-2)之氧透過度及透濕度。結果係如表1所示。 An ink layer was formed on the obtained multilayered structure (1-1-1), and it was allowed to stand at 40°C for 1 day for etching. Subsequently, an adhesive layer is formed, and ONY is laminated on the adhesive layer to prepare a laminate. Next, after forming an adhesive layer on the ONY of the laminate, CPP70 was laminated on the adhesive layer, and it was etched by standing at 40°C for 5 days. In this way, a multilayer structure (1-1-2) having a structure of the substrate (X-1)/layer (Y-1-1)/ink layer/adhesive layer/ONY/adhesive layer/CPP can be formed . Using a bar coater, coat the two adhesive layers with a thickness of 3 μm after drying to apply a 2-liquid type joint. The agent is formed after drying. The two-component adhesive is "A-525S" (trademark) using "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-50" (registered trademark) using "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. "(Trademark) and the formed two-liquid reactive polyurethane adhesive. In addition, the aforementioned ink layer is formed by coating with a bar coater so that the thickness after drying is 2 μm, and drying. The ink used "F641" (registered trademark) "F641STAR white" (trademark) manufactured by Toyo Ink Co., Ltd. and "LP Super Hardener" (trademark) manufactured by Toyo Ink Co., Ltd. and the resulting ink. The oxygen permeability and moisture permeability of the multilayer structure (1-1-2) were measured. The results are shown in Table 1.
將多層結構體(1-1-2)經熱密封以製作袋(pouch),將水100g填充入袋內。隨後,對所得之袋,依以下條件進行殺菌處理(熱水存放式)。 The multilayer structure (1-1-2) was heat-sealed to make a pouch, and 100 g of water was filled in the pouch. Subsequently, the resulting bag was sterilized according to the following conditions (hot water storage type).
殺菌處理裝置:日阪製作所股份有限公司製Flavor Ace RSC-60 Sterilization treatment device: Flavor Ace RSC-60 manufactured by Nisaka Manufacturing Co., Ltd.
溫度:130℃ Temperature: 130℃
時間:30分鐘 Time: 30 minutes
壓力:0.21MPaG Pressure: 0.21MPaG
熱水處理後,立即由袋上切取測定用樣品,依上述方法測定該樣品之氧透過度、透濕度,及T型剝離強度。又,多層結構體(1-1-2)中,並未發現剝離等外觀不良現象。 Immediately after the hot water treatment, the measurement sample was cut from the bag, and the oxygen permeability, moisture permeability, and T-peel strength of the sample were measured according to the above method. In addition, in the multilayer structure (1-1-2), no appearance defects such as peeling were observed.
除將磷酸酯化物(BP)之磷酸酯化率RBP及塗佈量依表1內容變更以外,其他皆依與實施例1-1之多層結構體(1-1-2)為相同方法製作多層結構體(1-2-2)~(1-6-2),並進行評估。與實施例1-1相同般,多層結構體(1-2-2)~(1-6-2)中,並未發現剝離等外觀不良現象。 Except that the phosphate esterification rate R BP and coating amount of the phosphate ester (BP) were changed according to the content of Table 1, the multilayer structure (1-1-2) of Example 1-1 was used to produce the same method Multi-layer structure (1-2-2) ~ (1-6-2), and evaluate. As in Example 1-1, in the multilayer structures (1-2-2) to (1-6-2), no appearance defects such as peeling were observed.
除將磷酸酯化物(BP)變更為聚(甲基丙烯酸2-膦醯氧乙基)(PPEM)及聚(乙烯膦酸)(PVPA)以外,其他皆依表1內容,依與實施例1-1之多層結構體(1-1-2)為相同方法製作多層結構體(C1-1-2)~(C1-3-2),並進行評估。 Except that the phosphate ester compound (BP) was changed to poly(methacrylic acid 2-phosphonooxyethyl) (PPEM) and poly(vinylphosphonic acid) (PVPA), all others were in accordance with Table 1 and according to Example 1. The multi-layer structure (1-1-2) of -1 is a multi-layer structure (C1-1-2) to (C1-3-2) made by the same method and evaluated.
實施例及比較例之多層結構體之製造條件係如表1所示。 The manufacturing conditions of the multilayer structure of Examples and Comparative Examples are shown in Table 1.
將實施例1-1所製作之多層結構體(1-1-2)以寬400mm方式裁剪,以CPP層互相接觸進行熱密封之方式,供應於縱型製袋填充包裝機(ORIHIRO股份有限公司製)。經由縱型製袋填充包裝機,製得如圖1所示以合掌貼合形式貼合的縱製袋填充密封袋(2-1-3)(寬度160mm、長度470mm)。並測定縱製袋填充密封袋(2-1-3)之殺菌處理前之氧透過度及透濕度。其結果係如表2所示。經由將縱製袋填充密封袋(2-1-3)熱密封而製得袋(pouch),將300mL水填充入袋內。隨後,對所得之袋,依與實施例1-1相同條件下進行殺菌處理(熱水存放式)。 The multilayer structure (1-1-2) produced in Example 1-1 was cut with a width of 400 mm, and the CPP layers were in contact with each other for heat sealing, and supplied to a vertical bag-filling packaging machine (ORIHIRO Co., Ltd. system). A vertical bag-filling sealed bag (2-1-3) (width 160 mm, length 470 mm) was produced by a vertical-type bag-filling and packaging machine as shown in FIG. 1. And measure the oxygen permeability and moisture permeability of the vertical bag filled sealed bag (2-1-3) before sterilization treatment. The results are shown in Table 2. A pouch was prepared by heat-sealing a vertical bag-filled sealed bag (2-1-3), and 300 mL of water was filled into the bag. Subsequently, the resulting bag was subjected to sterilization treatment under the same conditions as in Example 1-1 (hot water storage type).
熱水處理後,立即由袋上切取測定用樣品,依上述方法測定該樣品之氧透過度、透濕度,及T型剝離強度。其結果係如表2所示。又,熱水處理後之樣品並未發現剝離等外觀不良現象。 Immediately after the hot water treatment, the measurement sample was cut from the bag, and the oxygen permeability, moisture permeability, and T-peel strength of the sample were measured according to the above method. The results are shown in Table 2. In addition, the samples after hot water treatment did not show any appearance defects such as peeling.
除使用實施例1-2~1-6及比較例1-1~1-3之多層結構體(1-2-2)~(1-6-2)及(C1-1-2)~(C1-3-2)替代多層結構體(1-1-2)以外,其他皆依與實施例2-1之製作縱製袋填充密封袋(2-1-3)之相同方式,製得縱製袋填充密封袋(2-2-3)~(2-6-3)及(C2-1-3)~(C2-3-3)。隨後,對所得之各縱製袋 填充密封袋,與實施例2-1相同般,進行各種項目之測定。其結果係如表2所示。 Except for using the multilayer structures (1-2-2)~(1-6-2) and (C1-1-2)~(Examples 1-2~1-6 and Comparative Examples 1-1~1-3 C1-3-2) Except for replacing the multilayer structure (1-1-2), the others are prepared in the same manner as in Example 2-1, where the vertical bag filled and sealed bag (2-1-3) is produced Bag-filling sealed bags (2-2-3)~(2-6-3) and (C2-1-3)~(C2-3-3). Subsequently, the resulting longitudinal bags The sealed bag was filled, and various items were measured in the same manner as in Example 2-1. The results are shown in Table 2.
將實施例1-1所製得之多層結構體(1-1-2)以寬200mm×130mm之方式裁剪,以CPP層為內側之方式將2片多層結構體重疊,將長方形外緣以5mm之寬度進行熱密封。其次,將寬30mm之鐵氟隆(登記商標)之薄片由開口部之端部挿入,於該狀態下進行熱密封。熱密封後,將鐵氟隆之薄片拔除,製得平袋(3-1-3)。測定平袋(3-1-3)之殺菌處理前之氧透過度及透濕度。其結果係如表3所示。 The multilayer structure (1-1-2) prepared in Example 1-1 was cut to a width of 200 mm × 130 mm, and two multi-layer structures were stacked with the CPP layer as the inner side, and the outer edge of the rectangle was 5 mm The width is heat sealed. Next, a sheet of Teflon (registered trademark) with a width of 30 mm is inserted through the end of the opening, and heat-sealed in this state. After heat sealing, the Teflon sheet was pulled out to obtain a flat bag (3-1-3). The oxygen permeability and moisture permeability of the flat bag (3-1-3) before sterilization treatment were measured. The results are shown in Table 3.
隨後,將水100mL填充入平袋(3-1-3)中,依與實施例1-1相同條件下進行殺菌處理(熱水存放式)。熱水處理後,立即由平袋切取測定用樣品,依上述方法測定該樣品之氧透過度、透濕度,及T型剝離強度。其結果係如表3所示。此時,熱水處理後之樣品並未發現剝離等外觀不良現象。 Subsequently, 100 mL of water was filled in a flat bag (3-1-3) and subjected to sterilization treatment under the same conditions as in Example 1-1 (hot water storage type). Immediately after hot water treatment, a sample for measurement was cut from a flat bag, and the oxygen permeability, moisture permeability, and T-peel strength of the sample were measured according to the above method. The results are shown in Table 3. At this time, the samples after hot water treatment did not show any appearance defects such as peeling.
除使用實施例1-2~1-6及比較例1-1~1-3所製得之多層結構體(1-2-2)~(1-6-2)及(C1-1-2)~(C1-3-2)替代多層結構體(1-1-2)以外,其他皆依與實施例3-1之平袋(3-1-3)之製作為相同方法,製得平袋(3-2-3)~(3-6-3)及(C3-1-3)~(C3-3-3)。所得之各平袋,與實施例3-1相同般,進行各種項目之測定。其結果係如表3所示。 Except for the use of the multilayer structures (1-2-2) to (1-6-2) and (C1-1-2 produced in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 )~(C1-3-2) except for the multi-layer structure (1-1-2), the others are made in the same way as the flat bag (3-1-3) of Example 3-1 Bags (3-2-3)~(3-6-3) and (C3-1-3)~(C3-3-3). The obtained flat bags were measured in the same manner as in Example 3-1. The results are shown in Table 3.
由實施例1-1所製得之多層結構體(1-1-2),切取2片120mm×100mm之多層結構體。隨後,將切出之2片多層結構體,以CPP層為內側之方式重疊,於將周邊熱密封的同時,並經由熱密封設置聚丙烯製之壺嘴(口栓構件)。依此方式,即製得具有與圖3相同構造之輸注液袋(4-1-3)。並測定輸注液袋(4-1-3)之殺菌處理前之氧透過度及透濕度。其結果係如表4所示。 For the multilayer structure (1-1-2) produced in Example 1-1, two pieces of 120 mm×100 mm multilayer structure were cut out. Subsequently, the two cut multilayer structures were stacked with the CPP layer as the inner side, and while heat sealing the periphery, a spout (mouth plug member) made of polypropylene was provided through heat sealing. In this way, an infusion solution bag (4-1-3) having the same structure as FIG. 3 is prepared. And measure the oxygen permeability and moisture permeability of the infusion solution bag (4-1-3) before sterilization treatment. The results are shown in Table 4.
隨後,將水100mL填充入輸注液袋(4-1-3)中,於與實施例2-1相同條件下進行殺菌處理(熱水存放式)。熱水處理後,立即由輸注液袋切取測定用樣品,依上述方法測定該樣品之氧透過度、透濕度,及T型剝離強度。其結果係如表4所示。此時,樣品並未發現剝離等外觀不良現象。 Subsequently, 100 mL of water was filled in the infusion solution bag (4-1-3), and sterilization treatment (hot water storage type) was performed under the same conditions as in Example 2-1. Immediately after hot water treatment, the measurement sample was cut from the infusion solution bag, and the oxygen permeability, moisture permeability, and T-peel strength of the sample were measured according to the above method. The results are shown in Table 4. At this time, no appearance defects such as peeling were observed in the samples.
除使用實施例1-2~1-6及比較例1-1~1-3所製得之多層結構體(1-2-2)~(1-6-2)及(C1-1-2)~(C1-3-2)替代多層結構體(1-1-2)以外,其他皆依與製作實施例4-1之輸注液袋(4-1-3)為相同之方法,製得輸注液袋(bag)(4-2-3)~(4-6-3)及(C4-1-3)~(C4-3-3)。所得之各輸注液袋,與實施例4-1相同般,進行各種項目之測定。其結果係如表4所 示。 Except for the use of the multilayer structures (1-2-2) to (1-6-2) and (C1-1-2 produced in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 )~(C1-3-2) except for the multi-layer structure (1-1-2), the others are prepared in the same way as the infusion solution bag (4-1-3) of Example 4-1. Infusion solution bags (bag) (4-2-3)~(4-6-3) and (C4-1-3)~(C4-3-3). The obtained infusion solution bags were subjected to the measurement of various items in the same manner as in Example 4-1. The results are shown in Table 4. Show.
由實施例1-1所製得之多層結構體(1-1-2),切取直徑100mm之圓形多層結構體,作為容器用之蓋材。又,容器本體,為準備一付有凸緣之容器(東洋製罐股份有限公司製、「Hiretoflex」(登記商標)、「HR78-84」(商品名))。該容器為具有上面直徑為78mm、高度為30mm之杯形狀。容器之上面為開放式,形成於其周邊之凸緣部之寬度為6.5mm。容器為以烯烴層/鋼層/烯烴層之3層層合物所構成。其次,將水填充於上述容器本體至幾乎滿杯,經 將蓋材熱密封於凸緣部結果,得付蓋之容器(5-1-3)。此時,將蓋材之CPP層以接觸凸緣部方式配置,將蓋材熱密封。由付蓋之容器(5-1-3)之蓋材切取一邊長度為4.5cm之正方形的測定用樣品,放置於10cm四方的鋁箔(厚度30μm)上經切開之直徑2.0cm的圓之上,將試料與鋁箔之間,使用2液硬化型環氧系接著劑予以密封。使用該樣品,測定殺菌處理前之氧透過度及透濕度。其結果係如表5所示。 For the multilayer structure (1-1-2) produced in Example 1-1, a circular multilayer structure with a diameter of 100 mm was cut out and used as a cover material for containers. In addition, the container body is intended to prepare a container with a flange (made by Toyo Can Co., Ltd., "Hiretoflex" (registered trademark), "HR78-84" (trade name)). The container has a cup shape with an upper diameter of 78 mm and a height of 30 mm. The upper surface of the container is open, and the width of the flange formed on the periphery is 6.5 mm. The container is composed of a three-layer laminate of olefin layer/steel layer/olefin layer. Secondly, fill the above-mentioned container body with water to almost full cup, after As a result of heat sealing the lid material to the flange portion, a container (5-1-3) with a lid can be obtained. At this time, the CPP layer of the cover material is arranged so as to contact the flange portion, and the cover material is heat-sealed. A sample for measurement of a square with a side length of 4.5 cm is cut from the cover material of the container with a lid (5-1-3), and placed on a 10 cm square aluminum foil (thickness 30 μm) on a cut circle with a diameter of 2.0 cm. The sample and the aluminum foil were sealed with a two-liquid curing type epoxy adhesive. Using this sample, the oxygen permeability and moisture permeability before sterilization treatment were measured. The results are shown in Table 5.
隨後,對於付蓋之容器(5-1-3),依與實施例1-1相同條件下進行殺菌處理(熱水存放式)。熱水處理後,立即由蓋材切取測定用樣品,與殺菌處理前相同般,測定該樣品之氧透過度及透濕度。並依上述方法測定T型剝離強度。其結果係如表5所示。此時,樣品並未發現剝離等外觀不良現象。 Subsequently, the covered container (5-1-3) was subjected to sterilization treatment under the same conditions as in Example 1-1 (hot water storage type). After the hot water treatment, the measurement sample was immediately cut from the cover material, and the oxygen permeability and the moisture permeability of the sample were measured in the same way as before the sterilization treatment. The T-peel strength was measured according to the above method. The results are shown in Table 5. At this time, no appearance defects such as peeling were observed in the samples.
除使用實施例1-2~1-6及比較例1-1~1-3所製得之多層結構體(1-2-2)~(1-6-2)及(C1-1-2)~(C1-3-2)替代多層結構體(1-1-2)以外,其他皆依製作實施例5-1之付蓋之容器(5-1-3)之方法為相同之方法,製得付蓋之容器(5-2-3)~(5-6-3)及(C5-1-3)~(C5-3-3)。所得各付蓋之容器,與實施例5-1相同般,進行各種項目之測定。其結果係如表5所示。 Except for the use of the multilayer structures (1-2-2) to (1-6-2) and (C1-1-2 produced in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 )~(C1-3-2) except for the multi-layer structure (1-1-2), the other methods are the same as the method of making the container (5-1-3) with the lid in Example 5-1, The containers with cover (5-2-3)~(5-6-3) and (C5-1-3)~(C5-3-3) were prepared. The obtained containers with respective lids were measured in the same manner as in Example 5-1. The results are shown in Table 5.
將2片之CPP100,分別使用棒狀塗佈機,以乾燥後之厚度達3μm之方式,塗佈2液型接著劑,並使其乾燥。2液型接著劑為使用三井化學股份有限公司製之「TAKALAKE」(登記商標)之「A-525S」與三井化學股份有限公司製之「TAKANATE」(登記商標)之「A-50」所形成之2液反應型聚胺基甲酸酯系接著劑。其次,將2片之CPP100與實施例1-1之多層結構體(1-1-1)層合,於40℃下靜置5日進行蝕刻。依此方式,可製得具有CPP/接著層/基材(X-1)/層(Y-1-1)/接著層/CPP之構造的多層標籤(6-1-2)。依上述方法測定所得多層標籤(6-1-2)之氧透過度及透濕度。其結果係如表6所示。 Two pieces of CPP100 were applied using a bar coater, and the two-component adhesive was applied and dried to a thickness of 3 μm after drying. Two-component adhesive is formed by using "A-525S" of "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-50" of "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. The two-liquid reactive polyurethane adhesive. Next, two pieces of CPP100 were laminated with the multilayer structure (1-1-1) of Example 1-1, and were left to stand at 40°C for 5 days for etching. In this way, a multilayer label (6-1-2) having a structure of CPP/adhesive layer/substrate (X-1)/layer (Y-1-1)/adhesive layer/CPP can be produced. The oxygen permeability and moisture permeability of the obtained multilayer label (6-1-2) were measured according to the above method. The results are shown in Table 6.
將多層標籤(6-1-2)配合容器成形鑄模之母模型部的內壁表面形狀予以切斷,裝設於母模型部之內壁表面。其次,將公模型部擠壓入母模型部。其次,將熔融之聚丙烯(日本POLYPRO股份有限公司製之「NOVATEC」(登記商標)之「EA7A」),於220℃下注入公模型部與母模型部之間的模槽中。如此,經由實施射出成形,而形成目的之容器(6-1-3)。容器本體之厚度為700μm、表面積為83cm2。容器外側全體被多層標籤(6-1-2)所被覆,連接孔重疊有多層標籤(6-1-2),容器外側並沒有沒被多層標籤(6-1-2)所被覆之處。此時,多層標籤並未發現層間剝離,容器(6-1-3)之外觀為良好。 The multilayer label (6-1-2) is cut in accordance with the shape of the inner wall surface of the female model part of the container forming casting mold, and mounted on the inner wall surface of the female model part. Next, squeeze the male model part into the female model part. Next, molten polypropylene ("EA7A" of "NOVATEC" (registered trademark) manufactured by Japan Polypro Co., Ltd.) was injected into the cavity between the male model part and the female model part at 220°C. In this way, by performing injection molding, the intended container (6-1-3) is formed. The thickness of the container body is 700 μm, and the surface area is 83 cm 2 . The entire outer side of the container is covered with a multi-layer label (6-1-2), and the connecting hole is overlaid with a multi-layer label (6-1-2). At this time, the multi-layer label was not peeled between layers, and the appearance of the container (6-1-3) was good.
除使用實施例1-2~1-6及比較例1-1~1-3所製得之多層結構體(1-2-1)~(1-6-1)及(C1-1-1)~(C1-3-1)替代多層結構體(1-1-1)以外,其他皆依與實施例6-1之多層標籤(6-1-2)之製作為相同之方法,製得多層標籤(6-2-2)~(6-6-2)及(C6-1-2)~(6-3-2)。其次,除使用(6-2-2)~(6-6-2)及(C6-1-2)~(6-3-2)替代實施例6-1之多層標籤(6-1-2)以外,其他皆依與容器(6-1-3)之製作為相同之方法,製得容器(6-2-3)~(6-6-3)及(C6-1-3)~(C6-3-3)。模內標籤容器(6-2-3)~(6-6-3)之外觀為良好。另一方面,所得模內標籤容器(C6-1-3)~(C6-3-3)並未發現層間剝離現象。所得各多層標籤,依與實施例6-1相同方法,進行各種項目之測 定。其結果係如表6所示。 Except for the use of the multilayer structures (1-2-1) to (1-6-1) and (C1-1-1 produced in Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3 )~(C1-3-1) except for the multilayer structure (1-1-1), the others are prepared in the same way as the multilayer label (6-1-2) of Example 6-1. Multi-layer labels (6-2-2)~(6-6-2) and (C6-1-2)~(6-3-2). Secondly, in addition to using (6-2-2)~(6-6-2) and (C6-1-2)~(6-3-2) instead of the multilayer label (6-1-2 of Example 6-1) ), all others are produced in the same way as the container (6-1-3). The containers (6-2-3)~(6-6-3) and (C6-1-3)~( C6-3-3). The appearance of the in-mold label containers (6-2-3) to (6-6-3) is good. On the other hand, in the obtained in-mold label containers (C6-1-3) to (C6-3-3), no delamination phenomenon was observed. The obtained multi-layer labels were tested for various items in the same way as in Example 6-1 set. The results are shown in Table 6.
於實施例1-1中,於多層結構體(1-1-1)上之層(Y)上形成接著層之後,將聚乙烯樹脂(密度;0.917g/cm3、熔體流動速率;8g/10分鐘)以厚度為20μm之方式,於295℃下擠壓塗覆層合於該接著層上。依此方式,即製得具有基材(X-1)/層(Y-1-1)/接著層(I-1)/聚乙烯之構造的層合體(7-1-2)。上述接著層(I-1),為使用棒狀塗佈機以乾燥後之厚度為0.3μm之方式塗佈2液型接著劑,經乾燥後而形成。該2液型接著劑為使用三井化學股份有限公司製之 「TAKALAKE」(登記商標)之「A-3210」與三井化學股份有限公司製之「TAKANATE」(登記商標)之「A-3070」所形成之2液反應型聚胺基甲酸酯系接著劑。 In Example 1-1, after forming an adhesive layer on the layer (Y) on the multilayer structure (1-1-1), a polyethylene resin (density; 0.917 g/cm 3 , melt flow rate; 8 g (/10 minutes) At a thickness of 20 μm, the coating layer was extrusion-coated at 295° C. on the adhesive layer. In this way, a laminate (7-1-2) having a structure of base material (X-1)/layer (Y-1-1)/adhesive layer (I-1)/polyethylene was prepared. The adhesive layer (I-1) is formed by coating a two-component adhesive with a bar coater so that the thickness after drying is 0.3 μm. The two-component adhesive is used for "A-3210" of "TAKALAKE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and "A-3070" for "TAKANATE" (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. The formed two-liquid reactive polyurethane adhesive.
依上述方法測定層合體(7-1-2)之氧透過度及透濕度。其結果係如表7所示。 The oxygen permeability and moisture permeability of the laminate (7-1-2) were measured according to the above method. The results are shown in Table 7.
除使用實施例1-2~1-6及比較例1-1~1-3之多層結構體(1-2-1)~(1-6-1)及(C1-1-1)~(C1-3-1)替代多層結構體(1-1-1)以外,其他皆依與實施例7-1相同方法,製得層合體(7-2-2)~(7-6-2)及(C7-1-2)~(C7-3-2)。層合體(C7-1-2)~(C7-3-2)於捲取時發現有一部份層間剝離。所得之各層合體,依與實施例7-1為相同之方法,對各項目進行測定。其結果係如表7所示。 In addition to using the multilayer structures (1-2-1) to (1-6-1) and (C1-1-1) to (1-2-1 to 1-6 and Comparative Examples 1-1 to 1-3) C1-3-1) Instead of the multi-layer structure (1-1-1), the others were all prepared in the same manner as in Example 7-1 to obtain laminates (7-2-2) to (7-6-2) And (C7-1-2)~(C7-3-2). The laminates (C7-1-2) ~ (C7-3-2) were found to have a partial delamination during winding. The obtained laminates were measured for each item in the same manner as in Example 7-1. The results are shown in Table 7.
於實施例3-1所製得之平袋(3-1-3)中,填充1.5%乙醇水溶液500mL,使用殺菌處理裝置(日阪製作所製、Flavor Ace RCS-60),於120℃、0.15MPaG下,於熱水中進行30分鐘之殺菌處理。由殺菌處理後之平袋切取測定用樣品,測定該樣品之氧透過度。該樣品之氧透過度為0.2mL/(m2.day.atm)。 The flat bag (3-1-3) prepared in Example 3-1 was filled with 500 mL of a 1.5% ethanol aqueous solution, and a sterilization treatment device (Flavor Ace RCS-60 manufactured by Nisaka Manufacturing Co., Ltd.) was used at 120°C, 0.15 Under MPaG, sterilize in hot water for 30 minutes. The sample for measurement was cut out from the flat bag after sterilization treatment, and the oxygen permeability of the sample was measured. The oxygen permeability of this sample was 0.2 mL/(m 2 .day.atm).
除使用其他填充物500mL替代1.5%乙醇水溶液500mL,填充於平袋(3-1-3)以外,其他皆依實施例8-1相同方法進行殺菌處理。隨後,由殺菌處理後之平袋切取測定用樣品,測定該樣品之氧透過度。其他填充物,例如,可使用1.0%乙醇水溶液(實施例8-2)、食用醋(實施例8-3)、pH2之枸橡酸水溶液(實施例8-4)、食用油(實施例8-5)、蕃茄醬(實施例8-6)、醬油(實施例8-7),及生薑醬(實施例8-8)。無論任一情形,於殺菌處理後的樣品之氧透過度為0.2mL/(m2.day.atm)。此外,實施例5-1所製作之付蓋之容器(5-1-3)中,為填充幾乎滿杯之橘子醬,其他皆依實施例8-1相同方法進行殺菌處理(實施例8-9)。由殺菌處理後的付蓋之容器的蓋材切取測定用之樣品,測定該樣品之氧透過度結果,得知氧透過度為0.2mL/(m2. day.atm)。 Except that 500 mL of other fillers were used instead of 500 mL of 1.5% ethanol aqueous solution and filled in a flat bag (3-1-3), the others were sterilized in the same manner as in Example 8-1. Subsequently, a sample for measurement was cut out from the flat bag after the sterilization treatment, and the oxygen permeability of the sample was measured. For other fillers, for example, a 1.0% ethanol aqueous solution (Example 8-2), edible vinegar (Example 8-3), a pH 2 aqueous solution of citric acid (Example 8-4), and edible oil (Example 8) -5), tomato paste (Example 8-6), soy sauce (Example 8-7), and ginger paste (Example 8-8). In any case, the oxygen permeability of the sample after sterilization treatment is 0.2mL/(m 2 .day.atm). In addition, in the container with a lid (5-1-3) prepared in Example 5-1, in order to fill the almost full cup of marmalade, the others are sterilized in the same manner as in Example 8-1 (Example 8- 9). A sample for measurement was cut out from the lid material of the container with a lid after sterilization treatment, and the oxygen permeability of the sample was measured to find that the oxygen permeability was 0.2 mL/(m 2 .day.atm).
由實施例8-1~8-9得知,本發明之包裝材料,即使於填充各種食品的狀態進行殺菌處理後,亦顯示良好的阻隔性能。 It is known from Examples 8-1 to 8-9 that the packaging material of the present invention shows good barrier performance even after sterilization treatment in a state filled with various foods.
將實施例6-1所使用的2液型接著劑,以乾燥後之厚度達3μm之方式塗佈於CPP60上,經使其乾燥後形成接著層。將此CPP與實施例1-1所製得之多層結構體(1-1-2)之PET層貼合,而得層合物(9-1-1)。隨後,將前述之2液反應型聚胺基甲酸酯系接著劑,以乾燥後之厚度達3μm之方式塗於ONY之上,經使其乾燥後形成接著層。隨後,將此ONY與層合物(9-1-1)貼合,而得具有CPP/接著層/多層結構體/接著層/ONY之構造的多層結構體(9-1-2)。 The two-component adhesive used in Example 6-1 was applied to CPP60 so that the thickness after drying was 3 μm, and the adhesive layer was formed after drying. This CPP was bonded to the PET layer of the multilayer structure (1-1-2) produced in Example 1-1 to obtain a laminate (9-1-1). Subsequently, the aforementioned two-liquid reactive polyurethane adhesive was applied to ONY in such a way that the thickness after drying was 3 μm, and the adhesive layer was formed after drying. Subsequently, this ONY was laminated with the laminate (9-1-1) to obtain a multilayer structure (9-1-2) having a structure of CPP/adhesive layer/multilayer structure/adhesive layer/ONY.
裁斷多層結構體(9-1-2),而得2片尺寸為70cm×30cm之層合體。該2片之層合體以CPP層相互為內面之方式貼合,將3側以10mm度進行熱密封,而製得3方袋(開口袋)。其次,由3方袋之開口部填充隔熱性之芯材,使用真空包裝機,於20℃、內部壓力10Pa之狀態,將3方袋密封。依此方式,製得真空隔熱體(9-1-3)。隔熱性之芯材為使用二氧化矽微粉末。將真空隔熱體(9-1-3)於40℃、15% RH之條件下放置360日之後,使用派藍 尼真空計測定真空隔熱體內部壓力結果,為37.0Pa。 The multilayer structure (9-1-2) was cut to obtain two laminates with a size of 70 cm × 30 cm. The two-piece laminate was bonded with the CPP layers as inner surfaces, and the three sides were heat-sealed at 10 mm to produce a three-sided bag (open bag). Next, the opening of the three-square bag is filled with a heat-insulating core material, and the three-square bag is sealed using a vacuum packaging machine at 20°C and an internal pressure of 10 Pa. In this way, a vacuum heat insulator (9-1-3) was prepared. The core material of heat insulation is silicon dioxide fine powder. After placing the vacuum heat insulator (9-1-3) at 40°C and 15% RH for 360 days, use Piran The Ni vacuum gauge measured the internal pressure of the vacuum insulation body and found to be 37.0 Pa.
由真空隔熱體(9-1-3)切取測定用樣品,對該樣品,測定其氧透過度及水蒸氣透過度。 The sample for measurement was cut out from the vacuum heat insulator (9-1-3), and the oxygen permeability and water vapor permeability of the sample were measured.
使用恆溫恆濕機,於大氣壓下、85℃、85% RH之氛圍下,進行將真空隔熱體(9-1-3)保管1,000小時之試驗(溫濕試驗)後,由真空隔熱體(9-1-3)切取測定用樣品,依上述方法測定該樣品之氧透過度、透濕度,及T型剝離強度。其結果係如表8所示。又,樣品並未發現剝離等外觀不良現象。 Using a constant temperature and humidity machine, under the atmospheric pressure, 85 ℃, 85% RH atmosphere, the vacuum insulation body (9-1-3) was stored for 1,000 hours test (temperature and humidity test), the vacuum insulation body (9-1-3) Cut out the sample for measurement, and measure the oxygen permeability, moisture permeability, and T-peel strength of the sample according to the above method. The results are shown in Table 8. In addition, the sample did not show any appearance defects such as peeling.
除使用實施例1-2~1-6及比較例1-1~1-3之多層結構體(1-2-2)~(1-6-2)及(C1-1-2)~(C1-3-2)替代多層結構體(1-1-2)以外,其他皆依與實施例9-1之真空隔熱體(9-1-3)之製作方法為相同方法,製得真空隔熱體(9-2-3)~(9-6-3)及(C9-1-3)~(C9-3-3)。所得之各真空隔熱體,與實施例9-1相同般,進行各項目之測定。其結果係如表8所示。 Except for using the multilayer structures (1-2-2)~(1-6-2) and (C1-1-2)~(Examples 1-2~1-6 and Comparative Examples 1-1~1-3 C1-3-2) Substitute for the multi-layer structure (1-1-2), the other method is the same as the manufacturing method of the vacuum heat insulator (9-1-3) of Example 9-1, and the vacuum is obtained Heat insulation (9-2-3)~(9-6-3) and (C9-1-3)~(C9-3-3). The vacuum insulation bodies obtained were measured in the same manner as in Example 9-1. The results are shown in Table 8.
於實施例1-1所製得之多層結構體(1-1-1)上形成接著層,於該接著層上層合丙烯酸樹脂薄膜(厚度50μm)而得層合物。隨後,於該層合物之多層結構體(1-1-1)上形成接著層後,使該層合物與PET50層合。依此方式,而可製得具有PET/接著層/基材(X-1)/層(Y-1-1)/接著層/丙烯酸樹脂薄膜之構成的保護薄片(10-1-2)。上述2個接著層,為將2液型接著劑以乾燥後之厚度達3μm之方式分別進行塗佈,經乾燥後而形成。2液型接著劑為使用三井化學股份有限公司製之「TAKALAKE」(登記商標)之「A-1102」與三井化學股份有限公司製之「TAKANATE」(登記商標)之「A-3070」所形成之2液反應型聚胺基甲酸
酯系接著劑。測定所得保護薄片(10-1-2)之氧透過度及透濕度。其結果係如表9所示。
An adhesive layer was formed on the multilayer structure (1-1-1) produced in Example 1-1, and an acrylic resin film (
隨後,有關所得保護薄片(10-1-2)之耐久性試驗為,使用恆溫恆濕試驗機,於大氣壓下、85℃、85% RH之氛圍下,進行1,000時間保管保護薄片之試驗(溫濕試驗)。試驗後之保護薄片,經測定氧透過度及透濕度之結果係如表9所示。又,該保護薄片之接著性評估結果係如表9所示。並未發現剝離等外觀不良現象。 Subsequently, the durability test of the obtained protective sheet (10-1-2) was to use a constant temperature and humidity testing machine under atmospheric pressure, 85°C, 85% RH atmosphere for 1,000 hours to store the protective sheet test (temperature Wet test). The protective sheet after the test, the results of measuring oxygen permeability and moisture permeability are shown in Table 9. In addition, the evaluation results of the adhesion of the protective sheet are shown in Table 9. No appearance defects such as peeling were found.
除使用實施例1-2~1-6及比較例1-1~1-3之多層結構體(1-2-1)~(1-6-1)及(C1-1-1)~(C1-3-1)替代多層結構體(1-1-1)以外,其他皆依與實施例10-1相同之方法製得保護薄片(10-2-2)~(10-6-2)及(C10-1-2)~(C10-3-2),並對所得各保護薄片進行評估。其結果係如表9所示。其與實施例10-1相同般,保護薄片(10-2-2)~(10-6-2),於溫濕試驗後並未發現剝離等外觀不良現象。另一方面,保護薄片(C10-1-2)~(C10-3-2)之溫濕試驗結果,發現層間產生部份剝離,且外觀不良。 In addition to using the multilayer structures (1-2-1) to (1-6-1) and (C1-1-1) to (1-2-1 to 1-6 and Comparative Examples 1-1 to 1-3) C1-3-1) The protective sheets (10-2-2) to (10-6-2) were prepared in the same way as in Example 10-1 except for replacing the multilayer structure (1-1-1) And (C10-1-2) ~ (C10-3-2), and evaluate the protective sheets obtained. The results are shown in Table 9. In the same way as in Example 10-1, the protective sheets (10-2-2) to (10-6-2) did not show any appearance defects such as peeling after the temperature and humidity test. On the other hand, as a result of the temperature and humidity tests of the protective sheets (C10-1-2) to (C10-3-2), it was found that partial peeling occurred between the layers and the appearance was poor.
使用實施例10-1所得之保護薄片(10-1-2)製作太陽電池模組。具體而言為,首先,將設置於10cm四方強化玻璃上的非晶質矽太陽電池晶胞,挾夾於厚度450μm之乙烯-乙酸乙烯酯共聚物薄膜中。其次,於該薄膜上,以保護薄片(10-1-2)之聚對苯二甲酸乙二酯層為外側之方式貼合保護薄片(10-1-2),而製得太陽電池模組。貼合方式為,於150℃下進行3分鐘真空吸引後,進行9分鐘壓著之方式實施。依此方式所製得之太陽電池模組,顯示出良好的作動性,即使經過長期間亦顯示出良好的電力輸出特性。 The protective sheet (10-1-2) obtained in Example 10-1 was used to produce a solar cell module. Specifically, first, an amorphous silicon solar cell unit provided on a 10 cm square strengthened glass is sandwiched in an ethylene-vinyl acetate copolymer film with a thickness of 450 μm. Secondly, on this film, the protective sheet (10-1-2) is laminated with the polyethylene terephthalate layer of the protective sheet (10-1-2) as the outer side, to produce a solar cell module . The lamination method was carried out by performing vacuum suction at 150° C. for 3 minutes and then pressing for 9 minutes. The solar cell module produced in this way shows good operability, and even after a long period of time, it shows good power output characteristics.
本發明,可利用於多層結構體及使用其之包 裝材料,及多層結構體之製造方法。依本發明之內容,可得到一種具有優良之層間接著性,即使殺菌處理後也不會產生剝離等外觀不良之多層結構體。又,使用本發明之多層結構體時,可得到優良之包裝材料。 The invention can be used in multi-layer structures and packages using the same Packing materials, and methods of manufacturing multilayer structures. According to the content of the present invention, it is possible to obtain a multilayer structure having excellent interlayer adhesion and no appearance defect such as peeling even after sterilization treatment. In addition, when the multilayer structure of the present invention is used, excellent packaging materials can be obtained.
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