TWI840500B - 積層聚酯膜 - Google Patents

積層聚酯膜 Download PDF

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Publication number
TWI840500B
TWI840500B TW109103435A TW109103435A TWI840500B TW I840500 B TWI840500 B TW I840500B TW 109103435 A TW109103435 A TW 109103435A TW 109103435 A TW109103435 A TW 109103435A TW I840500 B TWI840500 B TW I840500B
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TW
Taiwan
Prior art keywords
coating layer
polyester film
mass
seconds
urethane resin
Prior art date
Application number
TW109103435A
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English (en)
Other versions
TW202041375A (zh
Inventor
高木紀志
多喜博
瀧井功
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日商東洋紡股份有限公司
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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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
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    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
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    • B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
    • B29C48/9165—Electrostatic pinning
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    • B29C48/92—Measuring, controlling or regulating
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    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
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    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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Abstract

本發明提供一種透明性高、具有耐黏連性、對硬塗層之密接性及對UV油墨之密接性優異之積層聚酯膜。積層聚酯膜係於聚酯膜基材的至少一面具有塗佈層，前述塗佈層係由含有具聚碳酸酯結構之胺基甲酸酯樹脂、交聯劑、及聚酯樹脂之組成物所硬化而成，基於利用前述塗佈層之深度方向之元素分佈測定所得的氮元素之分佈曲線之最大值存在於與聚酯膜基材為相反側之塗佈層表面附近，於與聚酯膜基材為相反側之塗佈層表面適量存在聚碳酸酯結構。

Description

積層聚酯膜
本發明係關於一種積層聚酯膜。更詳細而言，本發明係關於一種具有最適於光學用、包裝用、標籤用等所有領域的易接著性之塗佈層的積層聚酯膜。
熱塑性樹脂膜、其中又以聚酯膜係具有機械性質、電氣性質、尺寸穩定性、透明性、耐化學品性等優異之性質，故而被廣泛地用於磁性記錄材料、包裝材料、太陽電池用途、平面顯示器等所用之抗反射膜、擴散片、稜鏡片等光學膜、標籤印刷用膜等。然而，在這些用途中於聚酯膜上塗佈積層其他材料之情形時，有根據所使用之材料不同而有時接著性差之缺點。
因此，作為對聚酯膜的表面賦予接著性之方法之一，已知有於聚酯膜的表面塗佈各種樹脂而設置具有易接著性能之塗佈層的方法。
先前，已知有藉由將共聚合聚酯樹脂與胺基甲酸酯樹脂用於塗佈層，而對硬塗加工、稜鏡透鏡加工等賦予易接著性之技術(專利文獻1)。然而，該先前技術存在耐黏連性不佳，對用於標籤印刷之UV(Ultraviolet；紫外線)油墨之密接性不充分之問題點。
另外，亦已知有藉由將胺基甲酸酯樹脂與封閉異氰酸酯用於塗佈層，而尤其對太陽電池用正面片製造時所用之硬塗加工賦予易接著性的技術(專利文獻2)。然而，該先前技術存在透明性低之問題點。
另一方面，已知有藉由將丙烯酸共聚物與具有噁唑啉基之聚合物用於塗佈層，而對標籤加工賦予易接著性的技術(專利文獻3)。然而，該先前技術存在對硬塗層之密接性不充分之問題點。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2000-229355號公報。
[專利文獻2]日本特開2016-015491號公報。
[專利文獻3]日本特開2004-82369號公報。
本發明係以該先前技術之課題為背景而成。亦即，本發明之目的在於提供一種透明性高、具有耐黏連性、對硬塗層之密接性及對UV油墨之密接性優異的積層聚酯膜。
本發明者於為了解決上述課題而對上述問題的原因等進行研究之過程中發現：若在聚酯膜基材的至少一面具有塗佈層(含有交聯劑、具聚碳酸酯結構之胺基甲酸酯樹脂、及聚酯樹脂)，該塗佈層內的氮原子比率、及與聚酯膜基材為相反側之該塗佈層表面的OCOO鍵比率滿足特定之條件之情形時，能夠解決本發明之課題，以至完成了本發明。
前述課題係能夠藉由以下之解決手段而達成。
1.一種積層聚酯膜，係於聚酯膜基材的至少一面具有塗佈層，並且，前述塗佈層係由含有具聚碳酸酯結構之胺基甲酸酯樹脂、交聯劑、及聚酯樹脂之組成物所硬化而成，針對前述塗佈層，基於利用X射線光電子分光法進行之深度方向之元素分佈測定所得的氮元素分佈曲線中，於將與聚酯膜基材為相反側之塗佈層表面的氮原子比率設為A(at%)，將氮原子比率之最大值設為B(at%)，將氮原子比率顯示最大值B(at%)之蝕刻時間設為b(秒)，將於b(秒)以後氮原子比率達到1/2B(at%)時之蝕刻時間設為c(秒)時，滿足下述式(i)至式(iii)，並且，於藉由X射線光電子分光法所測定之表面分析光譜中，將源自C1s光譜區域的各鍵種之波峰面積合計設為100(%)，將源自OCOO鍵之波峰面積設為X(%)時，滿足下述式(iv)。
(i)0.5
Figure 109103435-A0305-02-0004-14
B-A(at%)
Figure 109103435-A0305-02-0004-15
3；(ii)30
Figure 109103435-A0305-02-0004-16
b(秒)
Figure 109103435-A0305-02-0004-17
180；(iii)30
Figure 109103435-A0305-02-0004-18
c-b(秒)
Figure 109103435-A0305-02-0004-19
300；(iv)2.0
Figure 109103435-A0305-02-0004-20
X(%)
Figure 109103435-A0305-02-0004-21
10.0。
2.如上述第1所記載之積層聚酯膜，霧度為1.5(%)以下。
本發明之積層聚酯膜係透明性高，具有耐黏連性，對硬塗層之密接性、對UV油墨之密接性優異。尤其，低線量加工時之UV油墨密接性優異。
[圖1]係針對實施例2之積層聚酯膜，基於利用X射線光電子分光法進行之深度方向之元素分佈測定所得的氮元素之分佈曲線。
[圖2]係從基於利用X射線光電子分光法進行之深度方向之元素分佈測定所得的氮元素之分佈曲線來求出B-A、b及c-b之說明圖。
[圖3]係針對實施例5之積層聚酯膜，基於利用X射線光電子分光法進行之深度方向之元素分佈測定所得的氮元素之分佈曲線。
[圖4]係針對比較例6之積層聚酯膜，基於利用X射線光電子分光法進行之深度方向之元素分佈測定所得的氮元素之分佈曲線。
[圖5]係表示實施例6之積層聚酯膜之塗佈層表面區域之C1s光譜之分析結果的圖譜。
[圖6]係表示比較例1之積層聚酯膜之塗佈層表面區域之C1s光譜之分析結果的圖譜。
[聚酯膜基材]
於本發明中構成聚酯膜基材之聚酯樹脂除了聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚2,6-萘二甲酸乙二酯、聚對苯二甲酸三亞甲酯等以外，也可舉出將前述般之聚酯樹脂的二醇成分或二羧酸成分的一部分替換為以下般之共聚成分而成之共聚合聚酯樹脂，例如，作為共聚成分，能夠列舉：二乙二醇、新戊二醇、1,4-環己烷二甲醇、聚伸烷基二醇等二醇成分；或者己二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、5-鈉間苯二甲酸、2,6-萘二羧酸等二羧酸成分等。
於本發明中可較佳地使用之聚酯樹脂主要係選自聚對苯二甲酸乙二酯、聚對苯二甲酸三亞甲酯、聚對苯二甲酸丁二酯、聚2,6-萘二甲酸乙二酯。這些聚酯樹脂中，就物性與成本之平衡而言，最佳為聚對苯二甲酸乙二酯。另外，由這些聚酯樹脂構成之聚酯膜基材較佳為雙軸延伸聚酯膜，能夠提高耐化學品性、耐熱性、機械強度等。
作為製造聚酯樹脂時所用之用於縮聚之觸媒並無特別限定，三氧化銻為價廉且具有優異之觸媒活性之觸媒，故而較佳。另外，亦較佳為使用鍺化合物或鈦化合物。作為更佳之縮聚觸媒，可列舉：含有鋁及/或其化合物與酚系化合物之觸媒、含有鋁及/或其化合物與磷化合物之觸媒、含有磷化合物之鋁鹽之觸媒。
另外，本發明中之聚酯膜基材可為單層之聚酯膜，亦可為成分互不相同之2層構成，亦可為具有外層與內層之至少由3層所構成之聚酯膜基材。
[本發明中之特性值之說明]
本發明之積層聚酯膜較佳為於如上所述之聚酯膜基材的至少一面具有塗佈層。前述塗佈層係由含有具聚碳酸酯結構之胺基甲酸酯樹脂、交聯劑、及聚酯樹脂之組成物所硬化而成。此處，使用「組成物所硬化而成」之表述之原因在於：要準確地表述具聚碳酸酯結構之胺基甲酸酯樹脂、交聯劑、及聚酯樹脂藉由交聯劑形成交聯結構而硬化之狀態的化學組成係極為困難。而且，基於前述塗佈層之深度方向之元素分佈測定的氮元素分佈曲線之最大值存在於與聚酯膜基材為相反側之塗佈層表面附近之情況下，能夠實現透明性、耐黏連性、硬塗密接性之提高，從而較佳。進而，於與聚酯膜基材為相反側之塗佈層表面適量存在聚碳酸酯結構之情況下，能夠實現低線量加工時之UV油墨密接性之提高，從而較佳。
對上述積層聚酯膜中之塗佈層之特性加以說明。首先，藉由X射線光電子分光法(ESCA)來描繪基於塗佈層之深度方向之元素分佈測定所得的氮元素分佈曲線。亦即，光譜收集係每隔30秒進行直至蝕刻時間120秒為止，以 後每隔60秒進行。而且，如圖2所示，取自塗佈層表面之蝕刻時間(單位：秒)為橫軸，取氮原子之量相對於碳原子、氧原子、氮原子、矽原子之合計量之比率(氮原子比率，單位：at%)為縱軸，將與聚酯膜基材為相反側之塗佈層表面的氮原子比率設為A(at%)，將氮原子比率之最大值設為B(at%)，將氮原子比率顯示最大值B(at%)之蝕刻時間設為b(秒)，將於b(秒)以後氮原子比率達到1/2B(at%)時之蝕刻時間設為c(秒)。根據讀取之數據計算而求出B-A(at%)、c-b(秒)。與聚酯膜基材為相反側之塗佈層表面的氮原子比率A(at%)為蝕刻時間0(秒)時之氮原子比率。
而且，於自上述之基於塗佈層之深度方向之元素分佈測定所得的氮元素分佈曲線所讀取之各特性值處於以下之關係時，可獲得透明性、耐黏連性、硬塗密接性優異之積層聚酯膜。
(i)0.5
Figure 109103435-A0305-02-0007-22
B-A(at%)
Figure 109103435-A0305-02-0007-23
3.0；(ii)30
Figure 109103435-A0305-02-0007-24
b(秒)
Figure 109103435-A0305-02-0007-25
180；(iii)30
Figure 109103435-A0305-02-0007-26
c-b(秒)
Figure 109103435-A0305-02-0007-27
300。
B-A之下限較佳為0.5at%，更佳為0.6at%，特佳為0.7at%，尤佳為0.8at%，最佳為0.9at%。若為0.5at%以上，則具有強韌性之胺基甲酸酯樹脂成分量充足，可獲得耐黏連性而較佳。另外，硬塗密接性亦提高而較佳。B-A之上限較佳為3.0at%，更佳為2.9at%，特佳為2.8at%，尤佳為2.7at%，最佳為2.5at%。若為3.0at%以下，則霧度低，可獲得透明性而較佳。
b之下限較佳為30秒，若為30秒以上，則保持與聚酯膜基材為相反側之塗佈層表面之強韌性，可獲得耐黏連性而較佳。b之上限較佳為180秒，更佳為120秒，特佳為90秒，尤佳為60秒。若為180秒以下，則保持與聚酯膜基材為相反側之塗佈層表面之強韌性，耐黏連性變得良好而較佳。另外，硬塗密接性提高而較佳。
c-b之上限較佳為300秒，更佳為240秒，特佳為180秒。若為300秒以下，則塗佈層中之胺基甲酸酯樹脂成分不會過剩，霧度低，可獲得透明性而較佳。由於光譜收集係自測定開始每隔30秒進行直至蝕刻時間120秒為止，故c-b之下限成為30秒以上。
於本發明中，較佳為構成積層聚酯膜之塗佈層中之胺基甲酸酯樹脂中的聚碳酸酯結構部分大多數局部存在於與聚酯膜基材為相反側之塗佈層表面。原因在於：藉由適量之聚碳酸酯結構部分存在於該表面，而對紫外線硬化型(UV)油墨之密接性提高。另一方面亦發現，聚碳酸酯結構部分存在於該表面之情況下，有時柔軟性變高而耐黏連性未必充分。因此，如上文所述，自基於塗佈層之深度方向之元素分佈測定所得的氮元素分佈曲線所讀取之各特性值處於以下之關係時，可獲得亦具備透明性、耐黏連性、硬塗密接性之優異之積層聚酯膜。
(i)0.5
Figure 109103435-A0305-02-0008-28
B-A(at%)
Figure 109103435-A0305-02-0008-29
3.0；(ii)30
Figure 109103435-A0305-02-0008-30
b(秒)
Figure 109103435-A0305-02-0008-31
180；(iii)30
Figure 109103435-A0305-02-0008-32
c-b(秒)
Figure 109103435-A0305-02-0008-33
300。
於本發明之積層聚酯膜中，作為用以滿足上述(i)至(iii)之式的手段，能夠列舉：將形成塗佈層之具聚碳酸酯結構之胺基甲酸酯樹脂加以合成、聚合時，包含聚碳酸酯多元醇成分與聚異氰酸酯成分而進行合成、聚合，聚碳酸酯多元醇成分與聚異氰酸酯成分之質量比為0.5至2.5之範圍內，聚碳酸酯多元醇成分之分子量為500至1800，於將塗佈液中之聚酯樹脂、胺基甲酸酯樹脂及交聯劑的固形物總和設為100質量%時，交聯劑的固形物之含有率為10質量%至50質量%。此外，作為交聯劑使用封閉異氰酸酯，藉由使用3官能以上之具異氰酸酯基之封閉異氰酸酯，而能夠有效率地調節B-A。用以滿足前述(i)至 (iii)之式的手段於僅單獨採用任一個或兩個之情況下，通常難以達成(i)至(iii)之式，藉由將這些手段儘量全部採用，而能夠有效地滿足(i)至(iii)之式。
另外，如上所述，較佳為本發明中之塗佈層中之胺基甲酸酯樹脂中的聚碳酸酯結構部分大多數以一定比率存在於與聚酯膜基材為相反側之塗佈層表面。於本發明中，於藉由X射線光電子分光法所測定之表面分析光譜中，將源自C1s光譜區域的各鍵種之波峰面積合計設為100(%)，將源自(作為聚碳酸酯結構之)OCOO鍵之波峰面積設為X(%)，以波峰面積之百分率表示。
此處，表面區域的(作為聚碳酸酯結構之)OCOO鍵之比率X(%)係利用X射線光電子分光法(ESCA)進行評價。圖5、圖6分別為表示後述之實施例6、比較例1之積層聚酯膜之表面區域之C1s光譜之分析結果的圖譜之例。灰色實線表示C1s光譜之實測數據。將所得之實測光譜之波峰分離為多個波峰，根據各波峰位置及形狀來鑑定出對應於各波峰之鍵種。進而，能夠以源自各鍵種之波峰實施曲線擬合(curve fitting)，算出波峰面積。本發明中之塗佈層含有：具聚碳酸酯結構之胺基甲酸酯樹脂、以3官能以上之具異氰酸酯基之封閉異氰酸酯為代表的交聯劑、及聚酯樹脂，於該塗佈層之情形時，可檢測出表1之波峰(1)至波峰(6)之鍵種的波峰。表1之波峰(1)至波峰(6)之鍵種亦有時未必僅為表1中所示之鍵種，而是些許包含類似之鍵種。此處，於關於實施例6之圖5中，表1之(3)之C=O鍵波峰及(6)之π-π＊鍵波峰並未出現。另外，於關於比較例1之圖6中，表1之(3)之C=O鍵波峰及(5)之OCOO鍵波峰並未出現。可謂表面區域的OCOO鍵之比率X(%)係以百分率(%)表示將波峰(1)至波峰(6)之波峰面積總體設為100%時的波峰(5)之面積比率。
Figure 109103435-A0305-02-0010-1
源自OCOO鍵之波峰面積X(%)之較佳範圍如下。X之下限較佳為2.0%，更佳為2.5%，特佳為3.0%，尤佳為3.5%，最佳為4.0%。若為2.0%以上，則能夠有效地滿足油墨密接性而較佳。X之上限較佳為10.0%，更佳為9.0%，特佳為8.0%，尤佳為7.5%，最佳為7%。若為10.0%以下，則表層之柔軟性不會變得過高，容易獲得耐黏連性而較佳。
作為本發明之積層聚酯膜之製造方法，為了使基於前述C1s光譜區域之X特性值能夠有效地實現2.0%至10.0%之範圍，較佳為於將形成塗佈層之具聚碳酸酯結構之胺基甲酸酯樹脂加以合成、聚合時，聚碳酸酯多元醇成分與聚異氰酸酯成分之質量比為0.5以上，於將塗佈液中之聚酯樹脂、具聚碳酸酯結構之胺基甲酸酯樹脂及交聯劑的固形物之總和設為100質量%時，胺基甲酸酯樹脂含有率為5質量%至50質量%。
[塗佈層]
本發明之積層聚酯膜為了提高對硬塗層之密接性、對UV油墨之密接性，較佳為於該積層聚酯膜的至少單面，積層有由含有具聚碳酸酯結構之胺基甲酸酯樹脂、交聯劑、及聚酯樹脂之組成物所形成的塗佈層。塗佈層亦可設置於聚 酯膜的兩面，亦可僅設置於聚酯膜的單面，且於另一面設置不同種類之樹脂被覆層。
以下，對塗佈層之各組成加以詳述。
[胺基甲酸酯樹脂]
本發明中之具聚碳酸酯結構之胺基甲酸酯樹脂係至少具有源自聚碳酸酯多元醇成分及聚異氰酸酯成分之胺基甲酸酯鍵部分，進而根據需要含有鏈延長劑。
將本發明中之具聚碳酸酯結構之胺基甲酸酯樹脂加以合成、聚合時的聚碳酸酯多元醇成分與聚異氰酸酯成分之質量比(聚碳酸酯多元醇成分之質量/聚異氰酸酯成分之質量)之下限較佳為0.5，更佳為0.6，特佳為0.7，尤佳為0.8，最佳為1.0。若為0.5以上，則能夠將塗佈層表面的OCOO鍵之比率X有效率地調節為2%以上而較佳。將本發明中之具聚碳酸酯結構之胺基甲酸酯樹脂加以合成、聚合時的聚碳酸酯多元醇成分與聚異氰酸酯成分之質量比之上限較佳為2.5，更佳為2.2，特佳為2.0，尤佳為1.7，最佳為1.5。若為2.5以下，則塗佈層表面的OCOO鍵之比率X能夠有效率地調節為10%以下而較佳。進而，於基於利用X射線光電子分光法之深度方向之元素分佈測定所得的氮分佈曲線中，能夠將B-A有效地調節為0.5at%以上，能夠將c-b有效地調節為300秒以下。
將本發明中之具聚碳酸酯結構之胺基甲酸酯樹脂加以合成、聚合所使用的聚碳酸酯多元醇成分中，較佳為含有耐熱、耐水解性優異之脂肪族系聚碳酸酯多元醇。作為脂肪族系聚碳酸酯多元醇，可列舉脂肪族系聚碳酸酯二醇、脂肪族系聚碳酸酯三醇等，能夠較佳地使用脂肪族系聚碳酸酯二醇。作為將本發明中之具聚碳酸酯結構之胺基甲酸酯樹脂加以合成、聚合所使用的脂肪 族系聚碳酸酯二醇，例如可列舉：藉由使乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,9-壬二醇、1,8-壬二醇、新戊二醇、二乙二醇、二丙二醇等二醇類之一種或兩種以上來與例如碳酸二甲酯、碳酸伸乙酯、光氣等碳酸酯類反應而獲得之脂肪族系聚碳酸酯二醇等。
作為本發明中之前述聚碳酸酯多元醇之數量平均分子量，較佳為500至1800。更佳為600至1700，最佳為700至1500。若為500以上，則塗佈層表面的OCOO鍵之比率X能夠有效地調節為10%以下而較佳。若為1800以下，則於基於利用X射線光電子分光法之深度方向之元素分佈測定所得的氮分佈曲線中，能夠將B-A有效地調節為0.5以上，將c-b有效地調節為300秒以下而較佳。
作為本發明中之具聚碳酸酯結構之胺基甲酸酯樹脂的合成、聚合所用之聚異氰酸酯，例如可列舉：二甲苯二異氰酸酯等芳香族脂肪族二異氰酸酯類；異佛酮二異氰酸酯及4,4-二環己基甲烷二異氰酸酯、1,3-雙(異氰酸酯甲基)環己烷等脂環式二異氰酸酯類；六亞甲基二異氰酸酯及2,2,4-三甲基六亞甲基二異氰酸酯等脂肪族二異氰酸酯類；或者使這些化合物以單一或多種與三羥甲基丙烷等預先加成而得之聚異氰酸酯類。於使用前述芳香族脂肪族二異氰酸酯類、脂環式二異氰酸酯類、或脂肪族二異氰酸酯類等之情形時，並無黃變之問題而較佳。另外，不會過度成為強硬之塗膜，能夠緩和由聚酯膜基材之熱收縮所致之應力，接著性變得良好而較佳。
作為鏈延長劑，可列舉：乙二醇、二乙二醇、1,4-丁二醇、新戊二醇及1,6-己二醇等二醇類；甘油、三羥甲基丙烷及季戊四醇等多元醇類；乙二 胺、六亞甲基二胺及哌嗪等二胺類；單乙醇胺及二乙醇胺等胺基醇類；硫代二乙二醇等硫代二-二醇類；或者水。
本發明中之塗佈層較佳為使用水系之塗佈液藉由後述之線上塗佈法設置。因此，本發明之胺基甲酸酯樹脂較理想為具有水溶性或水分散性。 再者，所謂前述「水溶性或水分散性」，係指對水或含有未達50質量%之水溶性有機溶劑的水溶液進行分散。
為了對胺基甲酸酯樹脂賦予水分散性，能夠於胺基甲酸酯分子骨架中導入(共聚)磺酸(鹽)基或羧酸(鹽)基。為了維持耐濕性，較佳為導入弱酸性之羧酸(鹽)基。另外，亦能夠導入聚氧伸烷基等非離子性基。
為了於胺基甲酸酯樹脂導入羧酸(鹽)基，例如導入作為多元醇成分之二羥甲基丙酸、二羥甲基丁酸等具有羧酸基之多元醇化合物來作為共聚成分，藉由鹽形成劑進行中和。作為鹽形成劑之具體例，可列舉：氨；三甲基胺、三乙基胺、三異丙基胺、三正丙基胺、三正丁基胺等三烷基胺類；N-甲基嗎啉、N-乙基嗎啉等N-烷基嗎啉類；N-二甲基乙醇胺、N-二乙基乙醇胺等N-二烷基烷醇胺類。這些能夠單獨使用，或也能夠併用兩種以上。
於為了賦予水分散性而使用具有羧酸(鹽)基之多元醇化合物作為共聚成分之情形時，較佳為於將胺基甲酸酯樹脂的總聚異氰酸酯成分設為100莫耳%時，胺基甲酸酯樹脂中的具有羧酸(鹽)基之多元醇化合物之組成莫耳比為3莫耳%至60莫耳%，較佳為5莫耳%至40莫耳%。於前述組成莫耳比未達3莫耳%之情形時，有時水分散性變困難。另外，於前述組成莫耳比超過60莫耳%之情形時，有時耐水性降低故而耐濕熱性降低。
本發明之胺基甲酸酯樹脂亦可為了提高強硬性而使封閉異氰酸酯鍵結於末端。
[交聯劑]
於本發明中，作為塗佈層形成用組成物所含有之交聯劑，較佳為封閉異氰酸酯，更佳為3官能以上之封閉異氰酸酯，尤佳為4官能以上之封閉異氰酸酯。藉由這些封閉異氰酸酯而耐黏連性、硬塗密接性提高。若使用封閉異氰酸酯交聯劑，則於基於利用X射線光電子分光法之深度方向之元素分佈測定所得的氮分佈曲線中，能夠將B-A有效地調節為0.5at%以上而較佳。
前述封閉異氰酸酯之封閉劑之沸點之下限較佳為150℃，更佳為160℃，特佳為180℃，尤佳為200℃，最佳為210℃。封閉劑之沸點越高，則即便受到塗佈液之塗佈後之乾燥步驟或當採用線上塗佈法之情形時的製膜步驟中之附加熱的影響，仍可抑制封閉劑之揮發，抑制微小之塗佈面凹凸之產生，膜之透明性提高。封閉劑之沸點之上限並無特別限定，但就生產性之方面而言，認為300℃左右為上限。沸點係與分子量有關，故而為了提高封閉劑之沸點，較佳為使用分子量大之封閉劑，封閉劑之分子量較佳為50以上，更佳為60以上，特佳為80以上。
封閉劑之解離溫度之上限較佳為200℃，更佳為180℃，特佳為160℃，尤佳為150℃，最佳為120℃。封閉劑會受到塗佈液之塗佈後之乾燥步驟或當採用線上塗佈法之情形時的製膜步驟中之附加熱的影響而與官能基解離，生成再生異氰酸酯基。因此，會與胺基甲酸酯樹脂等進行交聯反應而提高接著 性。於封閉異氰酸酯之解離溫度為上述溫度以下之情形時，封閉劑之解離充分進行，故而接著性變良好，尤其是耐濕熱性變良好。
作為用於本發明之封閉異氰酸酯的解離溫度為120℃以下且封閉劑之沸點為150℃以上之封閉劑，可列舉：重亞硫酸鹽系化合物：重亞硫酸鈉等；吡唑系化合物：3,5-二甲基吡唑、3-甲基吡唑、4-溴-3,5-二甲基吡唑、4-硝基-3,5-二甲基吡唑等；活性亞甲基系：丙二酸二酯(丙二酸二甲酯、丙二酸二乙酯、丙二酸二正丁酯、丙二酸二2-乙基己酯)、甲基乙基酮等；三唑系化合物：1,2,4-三唑等。其中，就耐濕熱性、黃變之方面而言，較佳為吡唑系化合物。
作為本發明之封閉異氰酸酯之前驅物的聚異氰酸酯係導入二異氰酸酯而獲得。例如可列舉：二異氰酸酯之胺基甲酸酯改性物、脲基甲酸酯改性物、脲改性物、縮二脲改性物、脲二酮改性物、脲亞胺改性物、異氰脲酸酯改性物、碳二醯亞胺改性物等。
作為二異氰酸酯，可列舉：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、2,4’-二苯基甲烷二異氰酸酯、2,2’-二苯基甲烷二異氰酸酯、1,5-萘二異氰酸酯、1,4-萘二異氰酸酯、苯二異氰酸酯、四甲基二甲苯二異氰酸酯、4,4’-二苯基醚二異氰酸酯、2-硝基二苯基-4,4’-二異氰酸酯、2,2’-二苯基丙烷-4,4’-二異氰酸酯、3,3’-二甲基二苯基甲烷-4,4’-二異氰酸酯、4,4’-二苯基丙烷二異氰酸酯、3,3’-二甲氧基二苯基-4,4’-二異氰酸酯等芳香族二異氰酸酯類；二甲苯二異氰酸酯等芳香族脂肪族二異氰酸酯類；異佛酮二異氰酸酯及4,4-二環己基甲烷二異氰酸酯、1,3-雙(異氰酸酯甲基)環己烷等脂環式二異氰酸酯類；六亞甲基二異氰酸酯及2,2,4-三甲基六亞甲基二異氰酸酯等脂肪族二異氰酸酯類。就透明性、接著性、耐濕熱性之方面而言，較佳為脂肪族異氰酸酯、 脂環式異氰酸酯或這些之改性物，作為並無黃變而要求高透明性之光學用途而較佳。
本發明中之封閉異氰酸酯為了賦予水溶性或水分散性而於作為前驅物之聚異氰酸酯導入親水基。作為親水基，可列舉：(1)二烷基胺基醇之四級銨鹽或二烷基胺基烷基胺之四級銨鹽等；(2)磺酸鹽、羧酸鹽、磷酸鹽等；(3)由烷氧基進行了單末端封鏈之聚乙二醇、聚丙二醇等。於導入了親水性部位之情形時，成為(1)陽離子性、(2)陰離子性、(3)非離子性。其中，其他水溶性樹脂係大多為陰離子性，故而較佳為能夠容易地相溶之陰離子性或非離子性。另外，陰離子性係與其他樹脂之相溶性優異，非離子性係不具有離子性之親水基，故而就提高耐濕熱性而言亦較佳。
作為陰離子性之親水基，較佳為具有用以導入至聚異氰酸酯之羥基、或是用以賦予親水性之羧酸基。例如可列舉：甘醇酸、乳酸、酒石酸、檸檬酸、氧基丁酸、氧基戊酸、羥基特戊酸、二羥甲基乙酸、二羥甲基丙酸、二羥甲基丁酸、具有羧酸基之聚己內酯。為了中和羧酸基，較佳為有機胺化合物。例如可列舉：氨；甲基胺、乙基胺、丙基胺、異丙基胺、丁基胺、2-乙基己基胺、環己基胺、二甲基胺、二乙基胺、二丙基胺、二異丙基胺、二丁基胺、三甲基胺、三乙基胺、三異丙基胺、三丁基胺、乙二胺等碳數1至20之直鏈狀、分支狀之一級胺、二級胺或三級胺；嗎啉、N-烷基嗎啉、吡啶等環狀胺；單異丙醇胺、甲基乙醇胺、甲基異丙醇胺、二甲基乙醇胺、二異丙醇胺、二乙醇胺、三乙醇胺、二乙基乙醇胺、三乙醇胺等含羥基之胺等。
作為非離子性之親水基，由烷氧基進行了單末端封鏈之聚乙二醇、聚丙二醇的環氧乙烷及/或環氧丙烷之重複單元較佳為3至50，更佳為5至30。 於重複單元小之情形時，與樹脂之相溶性變差，霧度上升，於重複單元大之情形時，有時高溫高濕下之接著性降低。本發明之封閉異氰酸酯為了提高水分散性而可添加非離子系、陰離子系、陽離子系、兩性界面活性劑。例如可列舉：聚乙二醇、多元醇脂肪酸酯等非離子系；脂肪酸鹽、烷基硫酸酯、烷基苯磺酸鹽、磺基琥珀酸鹽、烷基磷酸鹽等陰離子系；烷基胺鹽、烷基甜菜鹼等陽離子系；羧酸胺鹽、磺酸胺鹽、硫酸酯鹽等界面活性劑等。
另外，除了水以外，亦能夠含有水溶性之有機溶劑。例如，也能夠添加用於反應之有機溶劑，或將用於反應之有機溶劑去除而添加其他有機溶劑。
[聚酯樹脂]
用於形成本發明中之塗佈層之聚酯樹脂亦可為直鏈狀物，但更佳為以二羧酸與分支之二醇作為構成成分之聚酯樹脂。此處提及之二羧酸除了主成分為對苯二甲酸、間苯二甲酸或2,6-萘二羧酸以外，可列舉：己二酸、癸二酸等脂肪族二羧酸；對苯二甲酸、間苯二甲酸、鄰苯二甲酸、2,6-萘二羧酸等芳香族二羧酸。另外，所謂分支之二醇，為具有經分支之烷基的二醇，例如可列舉：2,2-二甲基-1,3-丙二醇、2-甲基-2-乙基-1,3-丙二醇、2-甲基-2-丁基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-甲基-2-異丙基-1,3-丙二醇、2-甲基-2-正己基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-乙基-2-正丁基-1,3-丙二醇、2-乙基-2-正己基-1,3-丙二醇、2,2-二正丁基-1,3-丙二醇、2-正丁基-2-丙基-1,3-丙二醇、及2,2-二正己基-1,3-丙二醇等。
關於聚酯樹脂，可謂上述更佳態樣之分支之二醇成分較佳為以10莫耳%以上之比率含有於總二醇成分中，更佳為以20莫耳%以上之比率含有於總二醇成分中。作為上述化合物以外之二醇成分，最佳為乙二醇。若為少量，則亦可使用二乙二醇、丙二醇、丁二醇、己二醇或1,4-環己烷二甲醇等。
關於作為上述聚酯樹脂之構成成分的二羧酸，最佳為對苯二甲酸或間苯二甲酸。若為少量，則亦可添加其他二羧酸，特別是二苯基羧酸、2,6-萘二羧酸等芳香族二羧酸進行共聚。除了上述二羧酸以外，為了對共聚合聚酯系樹脂賦予水分散性，較佳為使5-磺基間苯二甲酸以1莫耳%至10莫耳%之範圍進行共聚，例如可列舉：磺基對苯二甲酸、5-磺基間苯二甲酸、4-磺基萘間苯二甲酸-2,7-二羧酸、5-(4-磺基苯氧基)間苯二甲酸及其鹽類等。
於將塗佈液中之聚酯樹脂、具聚碳酸酯結構之胺基甲酸酯樹脂及交聯劑的固形物之總和設為100質量%時，交聯劑之含有率之下限較佳為5質量%，更佳為7質量%，特佳為10質量%，最佳為12質量%。若為5質量%以上，則於基於利用X射線光電子分光法之深度方向之元素分佈測定所得的氮分佈曲線中，容易將B-A調節為0.5at%以上而較佳。交聯劑之含有率之上限較佳為50質量%，更佳為40質量%，更佳為35質量%，最佳為30質量%。若為50質量%以下，則於基於利用X射線光電子分光法之深度方向之元素分佈測定所得的氮分佈曲線中，容易將c-b調節為300秒以下而較佳。
於將塗佈液中之聚酯樹脂、具聚碳酸酯結構之胺基甲酸酯樹脂及交聯劑的固形物之總和設為100質量%時，具聚碳酸酯結構之胺基甲酸酯樹脂之含有率之下限較佳為5質量%。若為5質量%以上，則容易將塗佈層表面的OCOO鍵之比率X調節為2.0%以上而較佳。具聚碳酸酯結構之胺基甲酸酯樹脂之含有 率之上限較佳為50質量%，更佳為40質量%，特佳為30質量%，最佳為20質量%。若胺基甲酸酯樹脂之含有率為50質量%以下，則容易將塗佈層表面的OCOO鍵之比率X調節為10.0%以下而較佳。
於將塗佈液中之聚酯樹脂、胺基甲酸酯樹脂及交聯劑的固形物之總和設為100質量%時，聚酯樹脂含有率之下限較佳為10質量%，更佳為20質量%，特佳為30質量%，尤佳為35質量%，最佳為40質量%。若聚酯樹脂之含有率為10質量%以上，則塗佈層與聚酯膜基材之密接性變得良好而較佳。聚酯樹脂之含有率之上限較佳為70質量%，更佳為67質量%，特佳為65質量%，尤佳為62質量%，最佳為60質量%。若聚酯樹脂之含有率為70質量%以下，則硬塗加工後之硬塗膜之耐濕熱性變得良好而較佳。
[添加劑]
於本發明中之塗佈層中，亦可於不損及本發明功效之範圍內添加公知之添加劑，例如界面活性劑、抗氧化劑、耐熱穩定劑、耐候穩定劑、紫外線吸收劑、有機之助滑劑、顏料、染料、有機或無機之粒子、抗靜電劑、成核劑等。
於本發明中，為了提高塗佈層之耐黏連性而於塗佈層添加粒子亦為較佳態樣。作為本發明中含有於塗佈層中之粒子，例如為氧化鈦、硫酸鋇、碳酸鈣、硫酸鈣、二氧化矽、氧化鋁、滑石、高嶺土、黏土等或這些之混合物，進而可列舉與其他一般之無機粒子例如磷酸鈣、雲母、鋰蒙脫石、氧化鋯、氧化鎢、氟化鋰、氟化鈣等併用而成之無機粒子；或苯乙烯系、丙烯酸系、三聚氰胺系、苯并胍胺系、矽酮系等之有機聚合物系粒子等。
塗佈層中之粒子之平均粒徑(由掃描式電子顯微鏡(SEM)所得之個數基準之平均粒徑。以下相同)較佳為0.04μm至2.0μm，更佳為0.1μm至1.0μm。若惰性粒子之平均粒徑為0.04μm以上，則容易於膜表面形成凹凸，故而膜之潤滑性或捲取性等操作性提高，貼合時之加工性良好而較佳。另一方面，若惰性粒子之平均粒徑為2.0μm以下，則不易產生粒子之脫落而較佳。塗佈層中之粒子濃度較佳為於固形成分中為1質量%至20質量%。
關於粒子之平均粒徑之測定方法，利用下述方法進行測定：藉由掃描式電子顯微鏡對積層聚酯膜之剖面之粒子進行觀察，觀察30個粒子，以粒子之平均值作為平均粒徑。
只要滿足本發明之目的，則粒子之形狀並無特別限定，能夠使用球狀粒子、不定形之非球狀粒子。不定形之粒子之粒徑係能夠以圓近似徑進行計算。圓近似徑為將所觀察到之粒子之面積除以π，算出平方根並乘以2倍所得之值。
[積層聚酯膜之製造]
列舉使用聚對苯二甲酸乙二酯(Polyethylene terephthalate，以下有時簡稱為PET)膜基材之例對本發明之積層聚酯膜之製造方法進行說明，但當然不限定於此。
充分地真空乾燥PET樹脂後，供給於擠出機，將約280℃之熔融PET樹脂自T模以片狀熔融擠出至旋轉冷卻輥，藉由靜電施加法冷卻固化而獲得未延伸PET片。前述未延伸PET片可為單層構成，亦可為由共擠出法所得之多層構成。
針對所得之未延伸PET片，藉由實施單軸延伸或雙軸延伸而進行結晶配向。例如於雙軸延伸之情形時，利用經加熱至80℃至120℃之輥於長度方向延伸至2.5倍至5.0倍，獲得單軸延伸PET膜後，以夾頭(clip)握持膜之端部，導引至經加熱至80℃至180℃之熱風區，於寬度方向延伸至2.5倍至5.0倍。另外，於單軸延伸之情形時，於拉幅機內延伸至2.5倍至5.0倍。延伸後繼續導引至熱處理區，進行熱處理，完成結晶配向。
熱處理區之溫度之下限較佳為170℃，更佳為180℃。若熱處理區之溫度為170℃以上則硬化變得充分，黏連性於液體之水存在下變得良好而較佳，無需延長乾燥時間。另一方面，熱處理區之溫度之上限較佳為230℃，更佳為200℃。若熱處理區之溫度為230℃以下，則並無膜之物性降低之虞而較佳。
塗佈層能夠於膜之製造後或於製造步驟中設置。尤其就生產性之方面而言，較佳為將塗佈液塗佈於膜製造步驟之任意階段、亦即未經延伸或單軸延伸後之PET膜的至少單面，形成塗佈層。
用以將該塗佈液塗佈於PET膜之方法能夠使用公知之任意方法。例如可列舉：逆輥塗佈法、凹版塗佈法、輕觸式塗佈法、模塗機法、輥刷法、噴霧塗佈法、氣刀塗佈法、線棒塗佈法、管式刮刀法、含浸塗佈法、簾幕式塗佈法等。能夠將這些方法單獨或組合進行塗敷。
於本發明中，塗佈層之厚度係能夠於0.001μm至2.00μm之範圍適當設定，但為了兼具加工性與接著性，較佳為0.01μm至1.00μm之範圍，更佳為0.02μm至0.80μm，特佳為0.05μm至0.50μm。若塗佈層之厚度為0.001μm以上，則接著性良好而較佳。若塗佈層之厚度為2.00μm以下，則不易產生黏連而較佳。
本發明之積層聚酯膜之霧度之上限較佳為1.5%，更佳為1.3%，特佳為1.2%，尤佳為1.0%。若霧度為1.5%以下，則於透明性之方面而言較佳，能夠適切使用於要求透明性之光學膜。
[實施例]
繼而，使用實施例及比較例對本發明加以詳細說明，但本發明不限定於以下之實施例。
[聚酯顆粒P-1之製造]
於附攪拌機之2L不鏽鋼製高壓釜裝入高純度對苯二甲酸及高純度對苯二甲酸之2倍莫耳量之乙二醇，相對於酸成分添加0.3莫耳%之三乙基胺，於0.25MPa之加壓下於250℃一邊將水蒸餾去除至系統外一邊進行酯化反應，獲得酯化率為約95%之對苯二甲酸雙(2-羥基乙基)酯及寡聚物之混合物(以下稱為BHET混合物)。繼而，一邊攪拌該BHET混合物，一邊以相對於聚酯中之酸成分以銻原子計成為0.04莫耳%之方式添加作為聚合觸媒之三氧化銻之乙二醇溶液，繼而於氮氣氛圍下，於常壓於250℃攪拌10分鐘。然後，耗費60分鐘一邊升溫至280℃一邊逐漸降低反應系統之壓力而設為13.3Pa(0.1Torr)，進而於280℃、13.3Pa實施縮聚反應。繼釋壓之後，將微加壓下之樹脂以繩股狀噴出至冷水並急遽冷卻，然後於冷水中保持20秒鐘後，切割而獲得長度約3mm、直徑約2mm之圓筒形狀之顆粒。
將藉由熔融聚合所得之聚酯顆粒減壓乾燥(13.3Pa以下、80℃、12小時)後，繼而進行結晶處理(13.3Pa以下、130℃、3小時，進而13.3Pa以下、160℃、3小時)。對於放置冷卻後之該聚酯顆粒，於固相聚合反應器內一邊將系 統內保持於13.3Pa以下、215℃一邊進行固相聚合，獲得固有黏度(溶劑：苯酚/四氯乙烷=60/40)為0.62dl/g之聚酯顆粒。
[鋁化合物之製備]
相對於在攪拌下於80℃進行2小時加熱處理而製備且確認到27Al-NMR(Nuclear Magnetic Resonance；核磁共振)光譜之波峰位置朝低磁場側化學位移之鹼性乙酸鋁(羥基鋁二乙酸鹽；Aldrich公司製造)之20g/l水溶液，將等量(體積比)之乙二醇一併裝入至燒瓶，於室溫攪拌6小時後，於減壓(133Pa)下、90℃至110℃一邊攪拌數小時一邊自系統中蒸餾去除水，製備20g/l之鋁化合物之乙二醇溶液。
[磷化合物之製備]
將作為磷化合物之Irganox 1222(汽巴精化(Ciba Specialty Chemicals)公司製造)與乙二醇一併放入至燒瓶，於氮氣置換下一邊攪拌一邊於液溫160℃加熱25小時，製備50g/l之磷化合物之乙二醇溶液。藉由31P-NMR光譜之測定確認到約60莫耳%變換為羥基。
[鋁化合物之乙二醇溶液/磷化合物之乙二醇溶液的混合物之製備]
將由上述鋁化合物之製備及上述磷化合物之製備所得之各乙二醇溶液裝入至燒瓶，以鋁原子與磷原子以莫耳比計成為1：2之方式於室溫混合，攪拌1天而製備觸媒溶液。該混合溶液之27Al-NMR光譜及31P-NMR光譜之測定結果係於任一情形時均確認到化學位移。
[聚酯顆粒P-2之製造]
作為縮聚觸媒，使用上述鋁化合物之乙二醇溶液/磷化合物之乙二醇溶液的混合物，以相對於聚酯中之酸成分以鋁原子及磷原子計分別成為0.014莫耳%及0.028莫耳%之方式添加，除此以外，進行與聚酯顆粒P-1之製造同樣之操作。獲得固有黏度(溶劑：苯酚/四氯乙烷=60/40)為0.65dl/g之聚酯顆粒P-2。
[具聚碳酸酯結構之胺基甲酸酯樹脂A-1之聚合]
於具備攪拌機、戴式冷凝器(Dimroth condenser)、氮氣導入管、矽膠乾燥管及溫度計之四口燒瓶，投入1,3-環己基二異氰酸酯32質量份、二羥甲基丙酸7質量份、數量平均分子量800之聚六亞甲基碳酸酯二醇58質量份、新戊二醇3質量份及作為溶劑之丙酮84.00質量份，於氮氣氛圍下於75℃攪拌3小時，確認反應液達到預定之胺當量。繼而，將該反應液降溫至40℃為止後，添加三乙基胺5.17質量份，獲得聚胺基甲酸酯預聚物溶液。繼而，於具備能高速攪拌之均質機之反應容器添加水450g，調整為25℃，一邊以2000min-1攪拌混合，一邊添加聚胺基甲酸酯預聚物溶液進行水分散。然後，於減壓下去除丙酮及水之一部分，藉此製備固形物34%之水分散性胺基甲酸酯樹脂溶液(A-1)。
[具聚碳酸酯結構之胺基甲酸酯樹脂A-2之聚合]
於具備攪拌機、戴式冷凝器、氮氣導入管、矽膠乾燥管及溫度計之四口燒瓶，投入4,4-二環己基甲烷二異氰酸酯38質量份、二羥甲基丙酸9質量份、數量平均分子量1000之聚六亞甲基碳酸酯二醇53質量份及作為溶劑之丙酮84.00 質量份，於氮氣氛圍下於75℃攪拌3小時，確認反應液達到預定之胺當量。繼而，將該反應液降溫至40℃為止後，添加三乙基胺5.17質量份，獲得聚胺基甲酸酯預聚物溶液。繼而，於具備能高速攪拌之均質機之反應容器添加水450g，調整為25℃，一邊以2000min-1攪拌混合，一邊添加聚胺基甲酸酯預聚物溶液進行水分散。然後，於減壓下去除丙酮及水之一部分，藉此製備固形物35%之水分散性胺基甲酸酯樹脂溶液(A-2)。
[具聚碳酸酯結構之胺基甲酸酯樹脂A-3之聚合]
於具備攪拌機、戴式冷凝器、氮氣導入管、矽膠乾燥管及溫度計之四口燒瓶，投入4,4-二環己基甲烷二異氰酸酯30質量份、數量平均分子量700之聚乙二醇單甲醚16質量份、數量平均分子量1200之聚六亞甲基碳酸酯二醇50質量份、新戊二醇4質量份及作為溶劑之丙酮84.00質量份，於氮氣氛圍下於75℃攪拌3小時，確認反應液達到預定之胺當量。繼而，將該反應液降溫至40℃為止後，獲得聚胺基甲酸酯預聚物溶液。繼而，於具備能高速攪拌之均質機之反應容器添加水450g，調整為25℃，一邊以2000min-1攪拌混合，一邊添加聚胺基甲酸酯預聚物溶液進行水分散。然後，於減壓下去除丙酮及水之一部分，藉此製備固形物35%之水分散性胺基甲酸酯樹脂溶液(A-3)。
[具聚碳酸酯結構之胺基甲酸酯樹脂A-4之聚合]
於具備攪拌機、戴式冷凝器、氮氣導入管、矽膠乾燥管及溫度計之四口燒瓶，投入4,4-二環己基甲烷二異氰酸酯24質量份、二羥甲基丁酸4質量份、數量平均分子量2000之聚六亞甲基碳酸酯二醇71質量份、新戊二醇1質量份及作 為溶劑之丙酮84.00質量份，於氮氣氛圍下於75℃攪拌3小時，確認反應液達到預定之胺當量。繼而，將該反應液降溫至40℃為止後，添加三乙基胺8.77質量份，獲得聚胺基甲酸酯預聚物溶液。繼而，於具備能高速攪拌之均質機之反應容器添加水450g，調整為25℃，一邊以2000min-1攪拌混合，一邊添加聚胺基甲酸酯預聚物溶液進行水分散。然後，於減壓下去除丙酮及水之一部分，藉此製備固形物34質量%之水分散性胺基甲酸酯樹脂溶液(A-4)。
[不含聚碳酸酯多元醇成分之胺基甲酸酯樹脂A-5之聚合]
藉由使用聚醚多元醇、有機聚異氰酸酯、作為鏈伸長劑之二乙二醇的多段式異氰酸酯聚加成方法，於70℃至120℃之溫度反應2小時。所得之胺基甲酸酯預聚物與重亞硫酸鹽水溶液混合，一邊充分攪拌約1小時一邊進行反應，進行封閉。反應溫度設為60℃以下。然後，以水稀釋，製備固形物20質量%之熱反應型水分散性胺基甲酸酯樹脂溶液(A-5)。
[具聚碳酸酯結構之胺基甲酸酯樹脂A-6之聚合]
於具備攪拌機、戴式冷凝器、氮氣導入管、矽膠乾燥管及溫度計之四口燒瓶，投入4,4-二環己基甲烷二異氰酸酯54質量份、數量平均分子量700之聚乙二醇單甲基醚16質量份、數量平均分子量1200之聚六亞甲基碳酸酯二醇18質量份、新戊二醇12質量份及作為溶劑之丙酮84.00質量份，於氮氣氛圍下於75℃攪拌3小時，確認反應液達到預定之胺當量。繼而，將該反應液降溫至40℃為止後，添加三乙基胺8.77質量份，獲得聚胺基甲酸酯預聚物溶液。繼而，於具備能高速攪拌之均質機之反應容器添加水450g，調整為25℃，一邊以2000min-1 攪拌混合，一邊添加聚胺基甲酸酯預聚物溶液進行水分散。然後，於減壓下去除丙酮及水之一部分，藉此製備固形物34質量%之水分散性胺基甲酸酯樹脂溶液(A-6)。
將下述2項目表示於表2。
A.將形成塗佈層之胺基甲酸酯樹脂加以合成、聚合時的聚碳酸酯多元醇成分與聚異氰酸酯成分之質量比(聚碳酸酯多元醇成分/聚異氰酸酯成分)
B.聚碳酸酯多元醇成分之分子量
Figure 109103435-A0305-02-0027-2
[封閉異氰酸酯交聯劑B-1之聚合]
於具備攪拌機、溫度計、回流冷凝管之燒瓶，對於以六亞甲基二異氰酸酯作為原料之具有異氰脲酸酯結構之聚異氰酸酯化合物(旭化成化學製造，Duranate TPA)66.04質量份、N-甲基吡咯啶酮17.50質量份滴加3,5-二甲基吡唑(解離溫度：120℃，沸點：218℃)25.19質量份，於氮氣氛圍下於70℃保持1小時。然後，滴加二羥甲基丙酸5.27質量份。測定反應液之紅外光譜，確認異氰酸酯基之吸收消失後，添加N,N-二甲基乙醇胺5.59質量份、水132.5質量份， 獲得固形物40質量%之封閉聚異氰酸酯水分散液(B-1)。該封閉異氰酸酯交聯劑之官能基數為4。
[封閉異氰酸酯交聯劑B-2之聚合]
於具備攪拌機、溫度計、回流冷凝管之燒瓶，裝入以六亞甲基二異氰酸酯作為原料之具有異氰脲酸酯結構之聚異氰酸酯化合物(旭化成化學製造，Duranate TPA)100質量份、丙二醇單甲醚乙酸酯55質量份、聚乙二醇單甲醚(平均分子量750)30質量份，於氮氣氛圍下於70℃保持4小時。然後，將反應液溫度下降至50℃，添加甲基乙基酮肟47質量份。測定反應液之紅外光譜，確認異氰酸酯基之吸收消失，獲得固形物40質量%之肟封閉異氰酸酯交聯劑(B-2)。該封閉異氰酸酯交聯劑之官能基數為3。
[碳二醯亞胺B-3之聚合]
於具備攪拌機、溫度計、回流冷凝器之燒瓶，裝入六亞甲基二異氰酸酯168質量份及聚乙二醇單甲醚(M400，平均分子量400)220質量份，於120℃攪拌1小時，進而添加4,4’-二環己基甲烷二異氰酸酯26質量份及作為碳二醯亞胺化觸媒之3-甲基-1-苯基-2-磷雜環戊烯-1-氧化物3.8質量份(相對於總異氰酸酯為2質量%)，於氮氣流下於185℃進而攪拌5小時。測定反應液之紅外光譜，確認波長220cm-1至2300cm-1之吸收消失。放置冷卻至60℃為止，添加離子交換水567質量份，獲得固形物40質量%之碳二醯亞胺水性樹脂液(B-3)。
[聚酯樹脂之聚合C-1]
於具備攪拌機、溫度計及局部回流式冷凝器之不銹鋼製高壓釜，裝入對苯二甲酸二甲酯194.2質量份、間苯二甲酸二甲酯184.5質量份、5-鈉磺基間苯二甲酸二甲酯14.8質量份、二乙二醇233.5質量份、乙二醇136.6質量份及鈦酸四正丁酯0.2質量份，於160℃至220℃之溫度耗費4小時進行酯交換反應。繼而升溫至255℃為止，將反應系統緩緩減壓後，於30Pa之減壓下反應1小時30分鐘，獲得共聚合聚酯樹脂(C-1)。所得之共聚合聚酯樹脂(C-1)為淡黃色透明。測定共聚合聚酯樹脂(C-1)之還原黏度，結果為0.70dl/g。由DSC(Differential Scanning Calorimeter；示差掃描熱析儀)所得之玻璃轉移溫度為40℃。
[聚酯水分散體之調整]
於具備攪拌機、溫度計及回流裝置之反應器加入聚酯樹脂(C-1)15質量份、乙二醇正丁醚15質量份，於110℃加熱、攪拌而溶解樹脂。樹脂完全溶解後，一邊攪拌一邊將水70質量份緩緩添加於聚酯溶液。添加後，一邊攪拌溶液一邊冷卻至室溫為止，製作固形物15質量%之乳白色之聚酯水分散體(Cw-1)。
[實施例1]
(1)塗佈液之製備
於水與異丙醇之混合溶劑中混合下述之塗劑，製成胺基甲酸酯樹脂溶液(A-1)/交聯劑(B-1)/聚酯水分散體(Cw-1)之固形物質量比成為25/26/49之塗佈液。
Figure 109103435-A0305-02-0029-3
Figure 109103435-A0305-02-0030-4
(2)積層聚酯膜之製造
作為膜原料聚合物，將固有黏度為0.62dl/g且實質上不含粒子之上述之聚酯顆粒(P-1)於133Pa之減壓下於135℃乾燥6小時。然後，供給於擠出機，於約280℃以片狀熔融擠出，於經保持於表面溫度20℃之旋轉冷卻金屬輥上急遽冷卻而密接固化，獲得未延伸PET片。
利用經加熱之輥群及紅外線加熱器將該未延伸PET片加熱至100℃，然後利用具有周速差之輥群於長度方向延伸3.5倍，獲得單軸延伸PET膜。
進而，利用輥塗佈法將於室溫靜置了5小時以上之前述塗佈液塗佈於PET膜的單面後，於80℃乾燥20秒鐘。再者，以最終(雙軸延伸後)之乾燥後之塗佈量成為0.15g/m2(乾燥後之塗佈層厚度150nm)之方式調整。繼而，利用拉幅機於120℃於寬度方向延伸至4.0倍，以固定膜之寬度方向之長度的狀態於230℃加熱5秒鐘，進而於100℃進行10秒鐘3%之寬度方向之鬆弛處理，獲得100μm之積層聚酯膜。將評價結果示於表5。
[實施例2]
除了將胺基甲酸酯樹脂變更為(A-2)以外，與實施例1同樣地獲得積層聚酯膜。
[實施例3]
除了將胺基甲酸酯樹脂變更為(A-3)以外，與實施例1同樣地獲得積層聚酯膜。
[實施例4]
除了將交聯劑變更為(B-2)以外，與實施例1同樣地獲得積層聚酯膜。
[實施例5]
於水與異丙醇之混合溶劑中混合下述之塗劑，以胺基甲酸酯樹脂溶液(A-1)/交聯劑(B-1)/聚酯水分散體(Cw-1)之固形物質量比成為22/10/68之方式變更，除此以外，與實施例1同樣地獲得積層聚酯膜。
Figure 109103435-A0305-02-0031-5
Figure 109103435-A0305-02-0032-6
[實施例6]
除了將胺基甲酸酯樹脂變更為(A-2)以外，與實施例5同樣地獲得積層聚酯膜。
如表5所示，實施例1至實施例6中，「B-A」、「b」、「c-b」分別滿足下述式之範圍，霧度、硬塗密接性、耐黏連性係能夠令人滿意。
(i)0.5
Figure 109103435-A0305-02-0032-34
B-A(at%)
Figure 109103435-A0305-02-0032-35
3.0；(ii)30
Figure 109103435-A0305-02-0032-36
b(秒)
Figure 109103435-A0305-02-0032-37
180；(iii)30
Figure 109103435-A0305-02-0032-38
c-b(秒)
Figure 109103435-A0305-02-0032-39
300。
另外，「X」滿足下述式，UV油墨密接性係能夠令人滿意。
(iv)2.0
Figure 109103435-A0305-02-0032-40
X(%)
Figure 109103435-A0305-02-0032-41
10.0。
[實施例7]
作為膜原料聚合物，將聚酯顆粒變更為上述之(P-2)，除此以外，與實施例1同樣地獲得積層聚酯膜。
如表5所示，於實施例7中，「B-A」、「b」、「c-b」分別滿足下述式之範圍，硬塗密接性、耐黏連性係能夠令人滿意。
(i)0.5
Figure 109103435-A0305-02-0032-42
B-A(at%)
Figure 109103435-A0305-02-0032-43
3.0；(ii)30
Figure 109103435-A0305-02-0032-44
b(秒)
Figure 109103435-A0305-02-0032-45
180；(iii)30
Figure 109103435-A0305-02-0032-46
c-b(秒)
Figure 109103435-A0305-02-0032-47
300。
另外，「X」滿足下述式，UV油墨密接性係能夠令人滿意。
(iv)2.0
Figure 109103435-A0305-02-0032-48
X(%)
Figure 109103435-A0305-02-0032-49
10.0。
進而確認到，與使用聚酯顆粒P-1之實施例1至實施例6相比較，霧度值小，膜之透明性提高。
[比較例1]
於水與異丙醇之混合溶劑中混合下述之塗劑，以胺基甲酸酯樹脂溶液(A-5)/聚酯水分散體(Cw-1)之固形物比成為29/71之方式變更，除此以外，與實施例1同樣地獲得積層聚酯膜。
Figure 109103435-A0305-02-0033-7
如表5所示，比較例1中，「X」未達2.0%，故而UV油墨密接性係無法令人滿意。另外，「b」超過180秒，故而耐黏連性亦無法令人滿意。
[比較例2]
除了將胺基甲酸酯樹脂變更為(A-4)以外，與實施例1同樣地獲得積層聚酯膜。
[比較例3]
除了將胺基甲酸酯樹脂變更為(A-4)，將交聯劑變更為(B-2)以外，與實施例1同樣地獲得積層聚酯膜。
如表5所示，於比較例2、比較例3中，「B-A」未達0.5at%，故而耐黏連性及硬塗密接性係無法令人滿意。
[比較例4]
於水與異丙醇之混合溶劑中混合下述之塗劑，以胺基甲酸酯樹脂溶液(A-4)/交聯劑(B-1)之固形物比成為70/30之方式變更，除此以外，與實施例1同樣地獲得積層聚酯膜。
Figure 109103435-A0305-02-0034-8
如表5所示，於比較例4中，「c-b」超過300秒，故而霧度係無法令人滿意。另外，「X」超過10.0%，故而耐黏連性係無法令人滿意。
[比較例5]
於水與異丙醇之混合溶劑中混合下述之塗劑，以胺基甲酸酯樹脂溶液(A-4)/交聯劑(B-1)之固形物比成為20/80之方式變更，除此以外，與實施例1同樣地獲得積層聚酯膜。
Figure 109103435-A0305-02-0035-9
如表5所示，於比較例5中，「c-b」超過300秒，故而霧度係無法令人滿意。
[比較例6]
除了將胺基甲酸酯樹脂變更為(A-2)，將交聯劑變更為(B-3)以外，與實施例5同樣地獲得積層聚酯膜。
如表5所示，於比較例6中，「B-A」未達0.5at%，故而耐黏連性及硬塗密接性係無法令人滿意。
[比較例7]
除了將胺基甲酸酯樹脂變更為(A-6)以外，與實施例5同樣地獲得積層聚酯膜。
如表5所示，於比較例7中，「X」未達2.0%，故而UV油墨密接性係無法令人滿意。
以下對本發明所用之評價方法進行說明。
(1)霧度
所得之積層聚酯膜之霧度係依據JIS(Japanese Industrial Standards；日本工業標準)K 7136：2000使用濁度計(日本電色製造，NDH5000)測定。
(2)耐黏連性
將2片膜試樣以塗佈層面彼此對向之方式重疊，施加98kPa之荷重，使該2片膜試樣於50℃之氛圍下密接並放置24小時。然後，剝離膜，按下述之基準判定膜之剝離狀態。
○：能夠無塗佈層之轉移且輕輕地剝離。
△：塗佈層得以維持，但塗佈層之表層局部地轉移至對象面。
×：2片膜固接而無法剝離，或者雖然能剝離但膜基材裂開。
(3)與UV油墨之密接性
於積層聚酯膜之塗佈層上，使用UV油墨[T＆K TOKA(股份有限公司)製造，商品名「BEST CURE UV161藍S」]，利用印刷機[明製作所(股份有限公司)製造，商品名「RI Tester」]實施印刷，繼而對塗佈了油墨層之膜使用高壓水銀燈照射40mJ/cm2之紫外線，使紫外線硬化型油墨硬化。繼而，使用間隙間隔2mm之切 刀導軌(cutter guide)，於油墨層面切出貫穿油墨層到達膜基材之100個網格狀之切口。繼而，將賽璐玢膠帶(米其邦(Nichiban)製造，405號；24mm寬)貼附於網格狀之切口面，以橡皮擦摩擦而使賽璐玢膠帶完全附著。然後，將賽璐玢膠帶垂直地自油墨積層膜之油墨層面剝下，藉由目視對自油墨積層膜之油墨層面剝落的網格之個數進行計數，由下述之式求出油墨層與膜基材之密接性。再者，網格中局部地剝離之網格亦作為剝落之網格進行計數。油墨密接性係將100(%)設為合格。
油墨密接性(%)=100-(剝落之網格之個數)。
(4)與硬塗層之密接性
於積層聚酯膜之塗佈層上，使用# 5線棒塗佈下述組成之硬塗層形成用塗佈液，於80℃乾燥1分鐘，去除溶劑。繼而，對塗佈了硬塗層之膜使用高壓水銀燈照射300mJ/cm2之紫外線，獲得硬塗膜。
[硬塗層形成用塗佈液]
Figure 109103435-A0305-02-0037-10
繼而，使用間隙間隔2mm之切刀導軌，於硬塗層面切出貫穿硬塗層到達膜基材之100個網格狀之切口。繼而，將賽璐玢膠帶(米其邦製造，405號；24mm寬)貼附於網格狀之切口面，以橡皮擦摩擦而使賽璐玢膠帶完全附著。然後，將賽璐玢膠帶垂直地自硬塗積層膜之硬塗層面剝下，對自硬塗積層膜之硬塗層面剝落的網格之個數進行計數，由下述之式求出硬塗層與膜基材之密接性。再者，網格中局部地剝離之網格亦作為剝落之網格進行計數。硬塗密接性係將95(%)設為合格。
硬塗密接性(%)=100-(剝落之網格之個數)。
(5)深度方向之元素分佈測定
塗佈層之深度方向之元素分佈測定係藉由X射線光電子分光法(ESCA)來進行。在進行蝕刻之離子源方面，使用對於有機材料能夠期待低損傷性之Ar簇(cluster)。另外，蝕刻時使試樣旋轉，以進行均勻之蝕刻。為了儘可能減少由X射線照射所致之損傷，於各蝕刻時間之光譜收集係以能以短時間進行評價之快照(snapshot)模式進行。另外，為了便於評價，光譜收集係每隔30秒進行直至蝕刻時間120秒為止，以後每隔60秒進行。測定條件之詳細顯示如下。再者，分析時，背景之去除係利用shirley法進行。
．裝置：K-Alpha+(Thermo Fisher Scientific公司製造)。
．測定條件
激發X射線：單色化Al Kα線
X射線輸出：12kV、2.5mA
光電子脫出角度：90°
點徑：200mmφ
通過能量：150eV(快照模式)
離子槍之加速電壓：6kV
簇尺寸：大(Large)
蝕刻速率：10nm/min(聚苯乙烯換算)*
蝕刻時之試樣旋轉：有
(於蝕刻速率之計算中，係使用將分子量Mn：91000(Mw/Mn=1.05)之單分散聚苯乙烯溶解於甲苯中後，藉由旋轉塗佈法於矽晶圓上製作之膜厚155nm之膜)。
基於以上述方式評價之數據，取自塗佈層表面之蝕刻時間為橫軸，取氮原子之量相對於碳原子、氧原子、氮原子、矽原子之合計量之比率(氮原子比率)為縱軸，描繪氮分佈曲線。將後述之積層聚酯膜試樣(實施例2、實施例5及比較例6)之氮分佈曲線分別示於圖1、圖3、圖4。使用圖2說明基於圖1所示之實施例2之氮分佈曲線求出本發明之特性值的方法。如圖2般，將與聚酯膜基材為相反側之塗佈層表面的氮原子比率設為A(at%)，將氮原子比率之最大值設為B(at%)，將氮原子比率達到最大值B(at%)之蝕刻時間設為b(秒)，將於b(秒)以後氮原子比率達到1/2B(at%)時之蝕刻時間設為c(秒)，讀取這些數據，計算求出B-A(at%)、c-b(秒)。所謂與聚酯膜基材為相反側之塗佈層表面的氮原子比率，係指圖之蝕刻時間0(秒)時之氮原子比率(再者，於圖1至圖4中之橫軸記載為「蝕刻時間s」之「s」係指單位之「秒」)。
(6)表面區域的OCOO鍵比率之測定
表面區域的OCOO鍵之比率(X)係藉由X射線光電子分光法(ESCA)進行評價。裝置係使用K-Alpha+(Thermo Fisher Scientific公司製造)。測定條件之詳細 如下。再者，分析時，背景之去除係藉由shirley法進行。另外，X之算出係設為3處以上之測定結果之平均值。
．測定條件
激發X射線：單色化Al Kα線
X射線輸出：12kV、6mA
光電子脫出角度：90°
點徑：400mmφ
通過能量：50eV
步長：0.1eV
能量解析度：Ag3d(5/2)光譜之FWHM=0.75eV。
圖5、圖6分別為表示實施例6、比較例1之積層聚酯膜之表面區域之C1s光譜之分析結果的圖譜。灰色實線表示C1s光譜之實測數據。將所得之實測光譜之波峰分離為多個波峰，根據各波峰位置及形狀來鑑定出對應於各波峰之鍵種。進而以源自各鍵種之波峰實施曲線擬合，算出波峰面積。將可能出現之各波峰(1)至波峰(6)之鍵種示於表3。
Figure 109103435-A0305-02-0040-11
所謂源自C1s光譜區域的各鍵種之波峰面積之合計，係指波峰(1)至波峰(6)的波峰面積之合計，所謂源自OCOO鍵之波峰面積，係指波峰(5)之波峰面積。於將源自C1s光譜區域之各鍵種的波峰面積之合計設為100%時，X(%)係以百分率表示波峰(5)之面積之比率(%)。
將實施例6及比較例1之波峰(1)至波峰(6)的波峰面積算出結果示於表4。如前文所述，波峰(5)之百分率數據為X(%)之數據。實施例6之波峰(3)、波峰(6)以及比較例1之波峰(3)、波峰(5)並未出現。
Figure 109103435-A0305-02-0041-12
(7)聚碳酸酯多元醇之數量平均分子量之測定方法
若藉由質子核磁共振光譜(1H-NMR)測定具有聚碳酸酯結構之胺基甲酸酯樹脂，則於4.1ppm附近觀測到源自鄰接於OCOO鍵之亞甲基的波峰。另外，於較該波峰高0.2ppm之磁場，觀測到源自鄰接於由聚異氰酸酯與聚碳酸酯多元醇之反應而產生的胺基甲酸酯鍵之亞甲基的波峰。根據這些兩種波峰之積分值及構成聚碳酸酯多元醇之單體之分子量來算出聚碳酸酯多元醇之數量平均分子量。
於表5整理各實施例、比較例之評價結果。
[表5]
Figure 109103435-A0305-02-0042-13
[產業可利用性]
根據本發明，能夠提供一種於光學用途、包裝用途、標籤用途等所有領域中能較佳地使用之積層聚酯膜。

Claims (2)

  1. 一種積層聚酯膜，係於聚酯膜基材的至少一面具有塗佈層，前述塗佈層係由含有具聚碳酸酯結構之胺基甲酸酯樹脂、交聯劑、及聚酯樹脂之組成物所硬化而成，針對前述塗佈層，基於利用X射線光電子分光法進行之深度方向之元素分佈測定所得的氮元素分佈曲線中，於將與聚酯膜基材為相反側之塗佈層表面的氮原子比率設為A(at%)，將氮原子比率之最大值設為B(at%)，將氮原子比率顯示最大值B(at%)之蝕刻時間設為b(秒)，將於b(秒)以後氮原子比率達到1/2B(at%)時之蝕刻時間設為c(秒)時，滿足下述式(i)至式(iii)，並且，於藉由X射線光電子分光法所測定之表面分析光譜中，將源自C1s光譜區域的各鍵種之波峰面積合計設為100(%)，將源自OCOO鍵之波峰面積設為X(%)時，滿足下述式(iv)： (i) 0.5 ≤ B－A(at%) ≤ 3.0； (ii) 30 ≤ b(秒) ≤ 180； (iii) 30 ≤ c－b(秒) ≤ 300； (iv) 2.0 ≤ X(%) ≤ 10.0。
  2. 如請求項1所記載之積層聚酯膜，霧度為1.5(%)以下。
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