TW202210601A - 接著劑、積層體、包裝材 - Google Patents
接著劑、積層體、包裝材 Download PDFInfo
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- TW202210601A TW202210601A TW110120029A TW110120029A TW202210601A TW 202210601 A TW202210601 A TW 202210601A TW 110120029 A TW110120029 A TW 110120029A TW 110120029 A TW110120029 A TW 110120029A TW 202210601 A TW202210601 A TW 202210601A
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- adhesive
- polyol
- film
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- 150000003384 small molecules Chemical class 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
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- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
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- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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Abstract
本發明提供一種耐蒸煮性、耐內容物性優異的層壓用接著劑、積層體、包裝材。一種接著劑、使用該接著劑而形成的積層體、包裝材,其中所述接著劑包含:含有聚異氰酸酯化合物(A1)的聚異氰酸酯組成物(A)、以及含有聚酯多元醇(B1)的多元醇組成物(B),聚酯多元醇(B1)是包含多元羧酸與多元醇的組成物的反應生成物,多元羧酸包含四聚酸。
Description
本發明是有關於一種接著劑、使用該接著劑獲得的積層體、包裝材。
作為食品、醫療品、化妝品、日用品等的包裝材料,可使用將鋁箔等金屬箔或金屬蒸鍍膜與聚乙烯、聚丙烯、氯乙烯、聚酯、尼龍等塑膠膜進行多層層壓並複合化而成的材料。該些積層體是根據各種用途中的要求特性將各種塑膠膜、金屬蒸鍍膜或金屬箔適宜組合並利用接著劑貼合而成的積層體。作為接著劑,一般可使用包含多元醇組成物與聚異氰酸酯組成物的二液硬化型的接著劑(例如專利文獻1)。
接著劑亦可根據內容物等適宜選擇。例如若為食品用途,則為了保護內容物免受各種流通、冷藏等保存或加熱殺菌等處理等的影響,可選擇製成包裝材時具有破袋強度或耐寒性、耐蒸煮性、耐熱性等功能的接著劑。若為洗滌劑或洗髮水、沐浴露等日用品用途,則可使用對內容物中所含的香料或界面活性劑等低分子量化合物的耐性優異的接著劑。
[現有技術文獻]
[專利文獻]
[專利文獻1]日本專利特開2014-101422號公報
[發明所欲解決之課題]
針對接著劑的該些特性的要求水準日益提高。例如於食品包裝的領域中,隨著飲食生活的提高這一時代潮流,食品的殺菌效率改善的動向正在高漲,進行熱水噴霧式蒸煮處理代替先前的熱水貯存式蒸煮處理的機會正在增加。熱水噴霧式蒸煮處理由於高溫高壓的熱水噴霧有時會直接接觸積層體,因此對接著劑要求比先前更高水準的耐蒸煮性。
另外,於日用品中,近年來隨著消費者的嗜好的變化,香味濃的製品、即香料的含量比先前多的製品亦變多,要求耐內容物性更優異的接著劑。
本發明是鑑於此種情況而成者,目的在於提供一種耐蒸煮性、耐內容物性優異的層壓用接著劑。
[解決課題之手段]
本發明者等人發現藉由如下接著劑可解決所述課題,所述接著劑包含:含有聚異氰酸酯化合物(A1)的聚異氰酸酯組成物(A)、以及含有聚酯多元醇(B1)的多元醇組成物(B),聚酯多元醇(B1)是包含多元羧酸與多元醇的組成物的反應生成物,多元羧酸包含四聚酸。
即,本發明是有關於一種接著劑,所述接著劑包含:含有聚異氰酸酯化合物(A1)的聚異氰酸酯組成物(A)、以及含有聚酯多元醇(B1)的多元醇組成物(B),聚酯多元醇(B1)是包含多元羧酸與多元醇的組成物的反應生成物,多元羧酸包含四聚酸。
[發明的效果]
根據本發明的接著劑,可提供耐蒸煮性、耐內容物性優異的接著劑、積層體、包裝材。
<接著劑>
本發明的接著劑包含:含有聚酯多元醇(A1)的多元醇組成物、以及含有聚異氰酸酯化合物(B1)的聚異氰酸酯組成物(B),聚酯多元醇(A1)是包含多元羧酸與多元醇的單體組成物的反應生成物,多元羧酸包含四聚酸。以下,對本發明的接著劑進行詳細說明。
(多元醇組成物(A))
本發明的接著劑中使用的多元醇組成物(A)含有聚酯多元醇(A1)。聚酯多元醇(A1)是包含多元羧酸與多元醇的單體組成物的反應生成物,多元羧酸包含四聚酸作為必需成分。
四聚酸是以油酸或亞麻油酸為代表的不飽和脂肪酸藉由狄爾斯-阿爾德反應(Diels-Alder reaction)而得的生成物,是使亞麻籽油脂肪酸、妥爾油脂肪酸、大豆油脂肪酸、米糠油脂肪酸、菜籽油脂肪酸、葵花籽油脂肪酸及包含該些脂肪酸的天然油的回收油中所含的不飽和脂肪酸反應而獲得的四官能羧酸。可為非環型、單環型、多環型、芳香環型的任一種,亦可為任意的兩種以上的組合。
關於本發明的接著劑的耐熱性、耐內容物性優異的理由,以如下方式推測。四聚酸的羧基與飽和烷基直接鍵結,自分支點至反應點(羧基)為止的距離亦長,因此不易受到立體阻礙的影響。再加上於較低的溫度下成為液體,四聚酸的羧基的反應性高,於酯化反應的初期優先被消耗。因此,以四聚酸為原料的聚酯多元醇(A1)成為含有具有以四聚酸為中心的星型的分支結構的聚酯多元醇(a1)者。藉由使用含有此種聚酯多元醇(A1)的多元醇組成物(A),接著劑的硬化塗膜成為含有大量的源自聚酯多元醇(a1)的分支點的、分支點濃度高者。源自聚酯多元醇(a1)的分支點即使於高溫環境下或水分、低分子量的移行物的存在下亦難以發生分解反應。因此,即使於高溫環境下或源自內容物的成分移行,亦可維持分支結構,抑制接著強度的降低。即,可製成耐熱性、耐蒸煮性、耐內容物性優異的接著劑。
進而,如上所述自四聚酸的分支點至反應點為止有距離,因此聚酯多元醇(a1)的酯鍵不會局部存在於源自四聚酸的分支點附近。因此,即使硬化塗膜的分支點濃度高亦可維持柔軟性,膜彼此的接著當然優異,鋁箔或鋁蒸鍍層、無機氧化物的蒸鍍層等相對硬的層與樹脂膜等相對軟的層的接著性亦優異。接著層亦可期待防止鋁蒸鍍層、無機氧化物的蒸鍍層等產生裂紋或發生剝離的緩衝作用。即使於硬化塗膜中浸入水分的情況下,分子鏈於分支點附近亦未被切斷過一次,因此可製成耐熱水性良好的接著劑。
作為用於製備聚酯多元醇(A1)的四聚酸以外的多元羧酸,可列舉:丙二酸、乙基丙二酸、二甲基丙二酸、琥珀酸、2,2-二甲基琥珀酸、琥珀酸酐、烯基琥珀酸酐、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、富馬酸、馬來酸、馬來酸酐、衣康酸、二聚酸、三聚酸等脂肪族多元羧酸;
丙二酸二甲酯、丙二酸二乙酯、琥珀酸二甲酯、戊二酸二甲酯、己二酸二甲酯、庚二酸二乙酯、癸二酸二乙酯、富馬酸二甲酯、富馬酸二乙酯、馬來酸二甲酯、馬來酸二乙酯等脂肪族多元羧酸的烷基酯化物;
1,1-環戊烷二羧酸、1,2-環戊烷二羧酸、1,3-環戊烷二羧酸、1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、四氫鄰苯二甲酸酐、4-甲基六氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、環己烷-1,2,4-三羧酸-1,2-酐、雙環庚烯二甲酸酐(himic anhydride)、氯橋酸酐等脂環族多元羧酸;
鄰苯二甲酸、對苯二甲酸、間苯二甲酸、鄰苯二甲酸酐、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、2,3-萘二羧酸酐、萘二甲酸(naphthalic acid)、1,2,4-苯三甲酸、1,2,4-苯三甲酸酐、均苯四甲酸、均苯四甲酸酐、聯苯二羧酸、1,2-雙(苯氧基)乙烷-p,p'-二羧酸、二苯甲酮四羧酸、二苯甲酮四羧酸二酐、5-鈉磺基間苯二甲酸、四氯鄰苯二甲酸酐、四溴鄰苯二甲酸酐等芳香族多元羧酸;
二甲基對苯二甲酸、2,6-萘二羧酸二甲酯等芳香族多元羧酸的甲酯化物等,可使用一種或組合兩種以上來使用。
用於製備聚酯多元醇(B1)的多元醇可為二醇,亦可為三官能以上的多元醇,所述二醇例如可列舉:乙二醇、二乙二醇、丙二醇、1,3-丙二醇、1,2,2-三甲基-1,3-丙二醇、2,2-二甲基-3-異丙基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、3-甲基-1,3-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-雙(羥基甲基)環己烷、2,2,4-三甲基-1,3-戊二醇、二聚物二醇等脂肪族二醇;
聚氧乙二醇、聚氧丙二醇等醚二醇;
藉由所述脂肪族二醇與環氧乙烷、環氧丙烷、四氫呋喃、乙基縮水甘油醚、丙基縮水甘油醚、丁基縮水甘油醚、苯基縮水甘油醚、烯丙基縮水甘油醚等各種含環狀醚鍵的化合物的開環聚合而獲得的改質聚醚二醇;
藉由所述脂肪族二醇與乳酸內酯(lactanoid)、ε-己內酯等各種內酯類的縮聚反應而獲得的內酯系聚酯多元醇;
雙酚A、雙酚F等雙酚;
雙酚A、雙酚F等雙酚上加成環氧乙烷、環氧丙烷等而獲得的雙酚的環氧烷加成物等。
所述三官能以上的多元醇可列舉:三羥甲基乙烷、三羥甲基丙烷、甘油、己三醇、季戊四醇等脂肪族多元醇;
藉由所述脂肪族多元醇與環氧乙烷、環氧丙烷、四氫呋喃、乙基縮水甘油醚、丙基縮水甘油醚、丁基縮水甘油醚、苯基縮水甘油醚、烯丙基縮水甘油醚等各種含環狀醚鍵的化合物的開環聚合而獲得的改質聚醚多元醇;
藉由所述脂肪族多元醇與ε-己內酯等各種內酯類的縮聚反應而獲得的內酯系聚酯多元醇等。
於單體組成物包含官能基間的最短的亞甲基鏈的碳原子數為6以上且20以下的化合物(b)、更具體而言包含具有多個羧基並且羧基間的最短的亞甲基鏈的碳原子數為6以上且20以下的脂肪族多元羧酸(b1)、或具有多個羥基並且羥基間的最短的亞甲基鏈的碳原子數為6以上且20以下的脂肪族多元醇(b2)時,接著劑的硬化塗膜變得更柔軟,對鋁蒸鍍層或無機氧化物層的密接性更優異,因此較佳。此種化合物(b)的調配量可根據接著劑所需的功能或其他單體適宜調整,作為一例為單體組成物的0.1質量%~35質量%。作為此種多元羧酸(b1)、多元醇(b2),可列舉:蓖麻油、二聚物二醇、辛二酸、壬二酸、癸二酸、二聚酸、三聚酸等。其中,較佳為二聚酸。再者,亞甲基鏈的碳原子數中不包含羧基的碳原子。另外,於在兩個官能基間除了亞甲基鏈以外還具有脂環結構或芳香環的情況下(例如二聚酸),形成該些環結構的碳原子亦不包含於亞甲基鏈中。於多元羧酸(b1)或多元醇(b2)具有三個以上的官能基的情況下,設為最短的官能基間的亞甲基鏈的碳原子數。
作為用於製備聚酯多元醇(A1)的四聚酸以外的多元羧酸、多元醇,亦較佳為使用均苯四甲酸、均苯四甲酸酐、山梨糖醇、季戊四醇、二季戊四醇等。該些單體可與四聚酸同樣地提高接著劑的硬化塗膜的分支點濃度。另一方面,該些單體自分支點至反應點為止的距離短,酯鍵集中於分支點附近,因此與使用四聚酸的情況不同,硬化塗膜的柔軟性存在降低的傾向。因此,較佳為與該些單體一起併用所述官能基間具有碳原子數為6以上且20以下的亞甲基鏈的多元羧酸(b1)或多元醇(b2)。於使用山梨糖醇的情況下,聚酯多元醇(A1)有著色之虞,於重視外觀的用途的情況下,較佳為自均苯四甲酸、均苯四甲酸酐、二聚酸、季戊四醇、二季戊四醇中適宜選擇使用。
聚酯多元醇(A1)亦可為除了所述多元羧酸及多元醇以外以聚異氰酸酯為必須原料的聚酯聚胺基甲酸酯多元醇(A1')。或者聚酯多元醇(A1)亦可為聚酯多元醇(A1)與聚酯聚胺基甲酸酯多元醇(A1')的混合物。用於製備聚酯聚胺基甲酸酯多元醇(A1')的聚異氰酸酯可將與作為後述的聚異氰酸酯化合物(B1)例示者相同者單獨使用或組合多種來使用。
聚酯聚胺基甲酸酯多元醇(A1')可為於合成聚酯多元醇作為前驅物後進行胺基甲酸酯伸長而成者,亦可為使包含多元羧酸、多元醇、聚異氰酸酯的單體組成物一併反應而成者。
四聚酸的調配量並無特別限制,作為一例,於用於合成聚酯多元醇(A1)的單體組成物總量中的調配量為0.1質量%以上時,耐熱性、耐內容物性容易提高而較佳。上限並無特別限制,但若過多,則於製造聚酯多元醇(A1)時容易發生凝膠化,製造難度變高,因此較佳為限制在單體組成物總量的4.0質量%以下。更佳為0.1質量%以上且2.0質量%以下。再者,於聚酯多元醇(A1)為聚酯聚胺基甲酸酯多元醇(A1')的情況下,單體組成物包含所述合成中使用的多元羧酸、多元醇、聚異氰酸酯。
聚酯多元醇(A1)的數量平均分子量(Mn)並無特別限定,作為一例為500~100,000,更佳為1,000~50,000。另外,重量平均分子量(Mw)作為一例為1,000~300,000,更佳為2,000~200,000。再者,本說明書中,數量平均分子量(Mn)、重量平均分子量(Mw)是藉由條件的凝膠滲透層析法(Gel Permeation Chromatography,GPC)測定的值。
測定裝置 :東曹股份有限公司製造的HLC-8320GPC
管柱 :東曹股份有限公司製造的TSKgel 4000HXL、TSKgel 3000HXL、TSKgel 2000HXL、TSKgel 1000HXL
檢測器 :RI(示差折射計)
資料處理 :東曹股份有限公司製造的多工位(Multi station)GPC-8020型號(model)II
測定條件 :管柱溫度 40℃
溶媒 四氫呋喃
流速 0.35 ml/分鐘
標準 :單分散聚苯乙烯
試樣 :藉由微濾器對以樹脂固體成分換算計為0.2質量%的四氫呋喃溶液進行過濾而成者(100 μl)
聚酯多元醇(A1)的羥基價較佳為1 mgKOH/g~150 mgKOH/g的範圍,更佳為3 mgKOH/g以上且為100 mgKOH/g以下。另外,聚酯多元醇(A1)的酸價並無特別限定,較佳為10.0 mgKOH/g以下。下限並無特別限制,作為一例為0.5 mgKOH/g以上。亦可為0 mgKOH/g。羥基價、酸價可藉由日本工業標準(Japanese Industrial Standard,JIS)-K0070中記載的方法測定。
多元醇組成物(A)亦可含有聚酯多元醇(A1)以外的多元醇(A2)。作為多元醇(A2),可列舉作為用於製備聚酯多元醇(A1)的多元醇而例示者。於多元醇組成物(B)含有多元醇(A2)的情況下,相對於聚酯多元醇(A1)與多元醇(A2)的調配量的合計100質量份,聚酯多元醇(A1)的調配量較佳為70質量份以上,更佳為80質量份以上,進而佳為90質量份以上。
(聚異氰酸酯組成物(B))
聚異氰酸酯組成物(B)含有聚異氰酸酯化合物(B1)。聚異氰酸酯化合物(B1)並無特別限制,可使用公知的化合物。作為此種聚異氰酸酯化合物(B1),可列舉:甲伸苯基二異氰酸酯、二苯基甲烷二異氰酸酯、聚合二苯基甲烷二異氰酸酯、1,5-萘二異氰酸酯、三苯基甲烷三異氰酸酯、伸二甲苯基二異氰酸酯等於分子結構內具有芳香族結構的聚異氰酸酯、利用碳二醯亞胺將該些聚異氰酸酯的NCO基的一部分改質而成的化合物;
異佛爾酮二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、1,3-(異氰酸基甲基)環己烷等於分子結構內具有脂環式結構的聚異氰酸酯;
1,6-六亞甲基二異氰酸酯、1,5-五亞甲基二異氰酸酯、離胺酸二異氰酸酯、三甲基六亞甲基二異氰酸酯等直鏈狀脂肪族聚異氰酸酯、利用碳二醯亞胺將該些聚異氰酸酯的NCO基的一部分改質而成的化合物;
該些聚異氰酸酯的異三聚氰酸酯體;該些聚異氰酸酯的脲甲酸酯體;該些聚異氰酸酯的縮二脲體;將該些聚異氰酸酯進行三羥甲基丙烷改質而成的加成物體;作為該些聚異氰酸酯與多元醇的反應生成物的聚胺基甲酸酯聚異氰酸酯等。
於使用聚胺基甲酸酯聚異氰酸酯作為聚異氰酸酯化合物(A1)的情況下,就接著劑塗膜的凝聚力與柔軟性的平衡的方面而言,較佳為使所述聚異氰酸酯與多元醇以異氰酸酯基與羥基的當量比[NCO]/[OH]為1.5~5.0的比例反應而獲得者。
作為用於製備聚胺基甲酸酯聚異氰酸酯的多元醇,可列舉: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、新戊二醇、甲基戊二醇、二甲基丁二醇、丁基乙基丙二醇、二乙二醇、三乙二醇、四乙二醇、二丙二醇、三丙二醇、雙羥基乙氧基苯等鏈狀脂肪族二醇;
1,4-環己二醇、1,4-環己烷二甲醇等脂環式二醇;
甘油、三羥甲基丙烷、季戊四醇等三官能或四官能的脂肪族醇;
雙酚A、雙酚F、氫化雙酚A、氫化雙酚F等雙酚;
二聚物二醇;
於所述二醇、三官能或四官能的脂肪族醇等聚合起始劑的存在下加成聚合環氧乙烷、環氧丙烷、環氧丁烷、苯環氧乙烷、表氯醇、四氫呋喃、伸環己基等環氧烷而成的聚醚多元醇;
藉由丙內酯、丁內酯、ε-己內酯、σ-戊內酯、β-甲基-σ-戊內酯等環狀酯化合物的開環聚合反應而獲得的聚酯與所述二醇或三官能或四官能的脂肪族醇的反應物、即聚酯多元醇(1);
使所述鏈狀脂肪族二醇、脂環式二醇、二聚物二醇、雙酚或所述聚醚多元醇等多元醇與多元羧酸反應而獲得的聚酯多元醇(2);
使所述三官能或四官能的脂肪族醇與多元羧酸反應而獲得的聚酯多元醇(3);
使二官能型多元醇、所述三官能或四官能的脂肪族醇與多元羧酸反應而獲得的聚酯多元醇(4);
二羥甲基丙酸、蓖麻油脂肪酸等羥基酸的聚合物、即聚酯多元醇(5);
所述聚酯多元醇(1)、聚酯多元醇(2)、聚酯多元醇(3)、聚酯多元醇(4)、聚酯多元醇(5)與聚醚多元醇的混合物;
蓖麻油、作為蓖麻油的氫化物的蓖麻硬化油、蓖麻油的環氧烷5莫耳~50莫耳加成體等蓖麻油系多元醇等,可單獨或組合多個來使用。
另外,作為用於製備聚酯多元醇(2)~聚酯多元醇(5)的多元羧酸,可使用與用於製備所述聚酯多元醇(A1)者相同者。
作為聚異氰酸酯化合物(B1),較佳為分子結構內具有芳香族結構的聚異氰酸酯、分子結構內具有芳香族結構的聚異氰酸酯的NCO基的一部分經碳二醯亞胺改質而成的化合物、分子結構內具有脂環式結構的聚異氰酸酯的任一者的異三聚氰酸酯體、脲甲酸酯體、縮二脲體、加成物體,更佳為甲伸苯基二異氰酸酯、1,6-六亞甲基二異氰酸酯、伸二甲苯基二異氰酸酯、異佛爾酮二異氰酸酯的異三聚氰酸酯體、脲甲酸酯體、縮二脲體、加成物體。
(接著劑的其他成分)
本發明的接著劑亦可含有所述成分以外的成分。該些成分可包含於聚異氰酸酯組成物(A)或多元醇組成物(B)中的任一者或兩者中,亦可與該些另行製備,於即將塗敷接著劑之前與聚異氰酸酯組成物(A)、多元醇組成物(B)一起混合使用。以下,對各成分進行說明。
(有機溶劑)
本發明的接著劑可為溶劑型或無溶劑型的任一種形態。本發明中所述的「溶劑型」的接著劑是指於將接著劑塗敷於基材後,利用烘箱等進行加熱而使塗膜中的有機溶劑揮發後與其他基材貼合的方法、所謂的乾式層壓法中使用的形態。聚異氰酸酯組成物(A)、多元醇組成物(B)中的任一者或兩者含有可溶解(稀釋)本發明中使用的聚異氰酸酯組成物(A)的構成成分、多元醇組成物(B)的構成成分的有機溶劑。
作為有機溶劑,例如可列舉:乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯等酯類、丙酮、甲基乙基酮、異丁基酮、環己酮等酮類、四氫呋喃、二噁烷等醚類、甲苯、二甲苯等芳香族烴類、氯化甲烷(Methylene chloride)、1,2-二氯乙烷等鹵化烴類、二甲基亞碸、二甲基磺醯二胺等。於製造聚異氰酸酯組成物(A)或多元醇組成物(B)的構成成分時作為反應介質使用的有機溶劑亦有時進而於塗裝時作為稀釋劑使用。
本說明書中,「無溶劑型」的接著劑是指聚異氰酸酯組成物(A)及多元醇組成物(B)實質上不包含如上所述般的溶解性高的有機溶劑、尤其是乙酸乙酯或甲基乙基酮而於不經過將接著劑塗敷於基材後利用烘箱等進行加熱來使溶劑揮發的步驟地與其他基材貼合的方法、所謂的無溶劑層壓法(nonsolvent laminate method)中使用的接著劑的形態。於無法完全去除聚異氰酸酯組成物(A)或多元醇組成物(B)的構成成分、或在其原料的製造時作為反應介質使用的有機溶劑而在聚異氰酸酯組成物(A)或多元醇組成物(B)中殘留有微量的有機溶劑的情況下,理解為實質上不包含有機溶劑。另外,於聚異氰酸酯組成物(A)含有低分子量醇的情況下,低分子量醇與多元醇組成物(B)反應而成為塗膜的一部分,因此於塗敷後不需要揮發。因此,此種形態亦視為無溶劑型接著劑,低分子量醇不視為有機溶劑。
(觸媒)
本發明的接著劑可根據需要藉由使用觸媒來促進硬化反應。作為觸媒,只要是促進聚異氰酸酯組成物(A)與多元醇組成物(B)的胺基甲酸酯化反應的觸媒,則並無特別限制,可例示金屬系觸媒、胺系觸媒、脂肪族環狀醯胺化合物、鈦螯合物錯合物等。
作為金屬系觸媒,可列舉金屬錯合物系、無機金屬系、有機金屬系的觸媒。作為金屬錯合物系的觸媒,可例示:選自由Fe(鐵)、Mn(錳)、Cu(銅)、Zr(鋯)、Th(釷)、Ti(鈦)、Al(鋁)、Co(鈷)所組成的群組中的金屬的乙醯丙酮鹽、例如乙醯丙酮鐵、乙醯丙酮錳、乙醯丙酮銅、乙醯丙酮氧化鋯等。就毒性與觸媒活性的方面而言,較佳為乙醯丙酮鐵(Fe(acac)3
)或乙醯丙酮錳(Mn(acac)2
)。
作為無機金屬系的觸媒,可列舉選自Sn、Fe、Mn、Cu、Zr、Th、Ti、Al、Co等中者。
作為有機金屬系觸媒,可列舉:辛酸鋅、新癸酸鋅、環烷酸鋅等有機鋅化合物、二乙酸亞錫(stannous diacetate)、二辛酸亞錫、二油酸亞錫、二月桂酸亞錫、二乙酸二丁基錫、二月桂酸二丁基錫、二月桂酸二辛基錫、二丁基氧化錫、二丁基二氯化錫等有機錫化合物、辛酸鎳、環烷酸鎳等有機鎳化合物、辛酸鈷、環烷酸鈷等有機鈷化合物、辛酸鉍、新癸酸鉍、環烷酸鉍等有機鉍化合物、四異丙氧基鈦酸酯、二丁基二氯化鈦、四丁基鈦酸酯、丁氧基三氯化鈦等鈦系化合物等。
作為胺系觸媒,可列舉:三伸乙基二胺、2-甲基三伸乙基二胺、啶(quinuclidine)、2-甲基啶、N,N,N',N'-四甲基伸乙基二胺、N,N,N',N'-四甲基伸丙基二胺、N,N,N',N'',N''-五甲基二伸乙基三胺、N,N,N',N'',N''-五甲基-(3-胺基丙基)伸乙基二胺、N,N,N',N'',N''-五甲基二伸丙基三胺、N,N,N',N'-四甲基六亞甲基二胺、雙(2-二甲基胺基乙基)醚、二甲基乙醇胺、二甲基異丙醇胺、二甲基胺基乙氧基乙醇、N,N-二甲基-N'-(2-羥基乙基)伸乙基二胺、N,N-二甲基-N'-(2-羥基乙基)丙二胺、雙(二甲基胺基丙基)胺、雙(二甲基胺基丙基)異丙醇胺、3-啶醇、N,N,N',N'-四甲基胍、1,3,5-三(N,N-二甲基胺基丙基)六氫-S-三嗪、1,8-二氮雜雙環[5.4.0]十一碳烯-7、N-甲基-N'-(2-二甲基胺基乙基)哌嗪、N,N'-二甲基哌嗪、二甲基環己胺、N-甲基嗎啉、N-乙基嗎啉、1-甲基咪唑、1,2-二甲基咪唑、1-異丁基-2-甲基咪唑、1-二甲基胺基丙基咪唑、N,N-二甲基己醇胺、N-甲基-N'-(2-羥基乙基)哌嗪、1-(2-羥基乙基)咪唑、1-(2-羥基丙基)咪唑、1-(2-羥基乙基)-2-甲基咪唑、1-(2-羥基丙基)-2-甲基咪唑等。
脂肪族環狀醯胺化合物例如可列舉:δ-戊內醯胺、ε-己內醯胺、ω-庚內醯胺(enantholactam)、η-辛內醯胺(capryllactam)、β-丙內醯胺等。該些中,ε-己內醯胺於促進硬化方面更有效。
鈦螯合物錯合物是可藉由紫外線照射提高觸媒活性的化合物,就硬化促進效果優異的方面而言,較佳為以脂肪族二酮或芳香族二酮為配位體的鈦螯合物錯合物。另外,本發明中,就本發明的效果變得更顯著的方面而言,較佳為除了芳香族二酮或脂肪族二酮以外具有碳原子數2~10的醇作為配位體者。
該些觸媒可單獨使用或組合兩種以上來使用。相對於聚異氰酸酯組成物(A)與多元醇組成物(B)的固體成分總量100質量份,觸媒的調配量較佳為設為0.001質量份~3質量份,更佳為設為0.01質量份~2質量份。
(顏料)
本發明的接著劑根據需要亦可含有顏料。作為所使用的顏料,並無特別限制,可列舉:「塗料原料便覽1970年度版」(日本塗料工業會編)中記載的體質顏料、白顏料、黑顏料、灰色顏料、紅色顏料、茶色顏料、綠色顏料、藍顏料、金屬粉顏料、發光顏料、珍珠色顏料等有機顏料或無機顏料、以及塑膠顏料等。
作為體質顏料,例如可列舉:沈降性硫酸鋇、白堊、沈降碳酸鈣、碳酸氫鈣、寒水石、氧化鋁白、二氧化矽、含水微粉二氧化矽(白碳)、超微粉無水二氧化矽(艾羅西爾(Aerosil))、矽砂(二氧化矽砂)、滑石、沈降性碳酸鎂、膨潤土、黏土、高嶺土、黃土等。
作為有機顏料的具體例,可列舉:聯苯胺黃、耐曬黃、色澱紅4R等各種不溶性偶氮顏料;色澱紅C、胭脂紅6B、棗紅(bordeaux)10等溶性偶氮顏料;酞菁藍、酞菁綠等各種(銅)酞菁系顏料;羅丹明色澱、甲基紫色澱等各種鹼性染色色澱;喹啉色澱、堅牢天藍等各種媒染染料系顏料;蒽醌系顏料、硫靛系顏料、紫環酮系顏料等各種建染染料系顏料;鮮貴紅B(Cinquasia RedB)等各種喹吖啶酮系顏料;二噁嗪紫等各種二噁嗪系顏料;克勞莫夫塔爾(Cromophtal)等各種縮合偶氮顏料;苯胺黑等。
作為無機顏料,可列舉:如黃鉛、鉻酸鋅、鉬橙等之類的各種鉻酸鹽;普魯士藍等各種亞鐵氰化物;氧化鈦、鋅華、瑪皮柯棕黃(mapico yellow)、氧化鐵、鐵丹、氧化鉻綠、氧化鋯等各種金屬氧化物;鎘黃、鎘紅、硫化汞等各種硫化物或硒化物;硫酸鋇、硫酸鉛等各種硫酸鹽;矽酸鈣、群青等各種矽酸鹽;碳酸鈣、碳酸鎂等各種碳酸鹽;鈷紫羅蘭、錳紫等各種磷酸鹽;鋁粉、金粉、銀粉、銅粉、青銅粉、黃銅粉等各種金屬粉末顏料;該些金屬的薄片顏料、雲母/薄片顏料;被覆有金屬氧化物的形態的雲母/薄片顏料、雲母狀氧化鐵顏料等金屬顏料或珠光顏料;石墨、碳黑等。
作為塑膠顏料,例如可列舉DIC(股)製造的「格蘭多(GRANDOLL)PP-1000」、「PP-2000S」等。
關於所使用的顏料,只要根據目的適宜選擇即可,例如就耐久性、耐侯性、設計性優異的方面而言,較佳為使用氧化鈦、鋅華等無機氧化物作為白色顏料,較佳為使用碳黑作為黑色顏料。
相對於聚異氰酸酯組成物(A)與多元醇組成物(B)的固體成分總量100質量份,顏料的調配量作為一例為1質量份~400質量份,為了使接著性、耐黏連性更良好,更佳為設為10質量份~300質量份。
(接著促進劑)
本發明的接著劑亦可包含接著促進劑。作為接著促進劑,可列舉:矽烷偶合劑、鈦酸酯系偶合劑、鋁系偶合劑等偶合劑、環氧樹脂等。
作為矽烷偶合劑,可列舉:γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)-γ-胺基丙基三甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷等胺基矽烷;β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷等環氧矽烷;乙烯基三(β-甲氧基乙氧基)矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等乙烯基矽烷;六甲基二矽氮烷、γ-巰基丙基三甲氧基矽烷等。
作為鈦酸酯系偶合劑,例如可列舉:四異丙氧基鈦、四-正丁氧基鈦、鈦酸丁酯二聚物、鈦酸四硬脂酯、乙醯丙酮鈦、乳酸鈦、四辛二醇鈦酸酯、四硬脂氧基鈦等。
作為鋁系偶合劑,例如可列舉乙醯烷氧基二異丙醇鋁等。
作為環氧樹脂,可列舉:一般市售的表雙(epibis)型、酚醛清漆型、β-甲基表氯型(β-methyl epichloro type)、環狀環氧乙烷型、縮水甘油醚型、縮水甘油酯型、聚二醇醚型、二醇醚型、環氧化脂肪酸酯型、多元羧酸酯型、胺基縮水甘油基型、間苯二酚型等各種環氧樹脂、或三縮水甘油基三(2-羥基乙基)異三聚氰酸酯、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、丙烯酸縮水甘油醚、2-乙基己基縮水甘油醚、苯基縮水甘油醚、苯酚縮水甘油醚、對第三丁基苯基縮水甘油醚、己二酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、甲基丙烯酸縮水甘油酯、丁基縮水甘油醚等化合物等。
(其他添加劑)
本發明的接著劑除了所述成分以外,亦可包含調平劑、膠體狀二氧化矽或氧化鋁溶膠等無機微粒子、聚甲基丙烯酸甲酯系的有機微粒子、消泡劑、流掛性防止劑、濕潤分散劑、黏性調整劑、紫外線吸收劑、金屬鈍化劑、過氧化物分解劑、阻燃劑、補強劑、塑化劑、潤滑劑、防鏽劑、螢光性增白劑、無機系熱線吸收劑、防焰劑、抗靜電劑、脫水劑、公知慣用的熱塑性彈性體、黏著賦予劑、磷酸化合物、三聚氰胺樹脂、反應性彈性體等。該些添加劑的調配量可於不損及本發明的接著劑的希望的範圍內適宜調整。
<積層體>
本發明的積層體可使用本發明的接著劑並藉由乾式層壓法或無溶劑層壓法將多個膜或紙貼合而獲得。所使用的膜並無特別限制,可根據用途適宜選擇膜。例如,作為食品包裝用,可列舉:聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)膜、聚苯乙烯膜、聚醯胺膜、聚丙烯腈膜、聚乙烯膜(LLDPE:低密度聚乙烯膜、HDPE:高密度聚乙烯膜)或聚丙烯膜(CPP:未拉伸聚丙烯膜、OPP:雙軸拉伸聚丙烯膜)等聚烯烴膜、聚乙烯醇膜、伸乙基-乙烯醇共聚物膜等。
膜亦可為實施了拉伸處理者。作為拉伸處理方法,一般是於利用擠出製膜法等將樹脂熔融擠出而形成片狀後,進行同時雙軸拉伸或逐次雙軸拉伸。另外,於逐次雙軸拉伸的情況下,一般是首先進行縱向拉伸處理,其次進行橫向拉伸。具體而言,大多採用將利用輥間的速度差的縱向拉伸與使用拉幅機的橫向拉伸組合的方法。
或者,亦可併用積層有鋁等金屬、二氧化矽或氧化鋁等金屬氧化物的蒸鍍層的膜、含有聚乙烯醇或伸乙基/乙烯醇共聚物、偏二氯乙烯等阻氣層的阻隔性膜。藉由使用此種膜,可製成對水蒸氣、氧、酒精、惰性氣體、揮發性有機物(香味)等具有阻隔性的積層體。
作為更具體的積層體的結構,可列舉:
(1)基材膜1/接著層1/密封劑膜
(2)基材膜1/接著層1/金屬蒸鍍未拉伸膜
(3)基材膜1/接著層1/金屬蒸鍍拉伸膜
(4)透明蒸鍍拉伸膜/接著層1/密封劑膜
(5)基材膜1/接著層1/基材膜2/接著層2/密封劑膜
(6)基材膜1/接著層1/金屬蒸鍍拉伸膜/接著層2/密封劑膜
(7)基材膜1/接著層1/透明蒸鍍拉伸膜/接著層2/密封劑膜
(8)基材膜1/接著層1/金屬層/接著層2/密封劑膜
(9)基材膜1/接著層1/基材膜2/接著層2/金屬層/接著層3/密封劑膜
(10)基材膜1/接著層1/金屬層/接著層2/基材膜2/接著層3/密封劑膜
等,但不限定於此。
作為結構(1)中可使用的基材膜1,可列舉OPP膜、PET膜、尼龍膜(以後亦稱為Ny膜)等。另外,作為基材膜1,亦可使用實施了以提高阻氣性或設置後述的印刷層時的油墨接受性等為目的的塗佈的基材膜。作為實施了塗佈的基材膜1的市售品,可列舉K-OPP膜或K-PET膜等。接著層1是本發明的接著劑的硬化塗膜。作為密封劑膜,可列舉CPP膜、LLDPE膜等。亦可於基材膜1的接著層1側的面(於使用實施了塗佈者作為基材膜1的情況下為塗佈層的接著層1側的面)設置印刷層。印刷層藉由凹版油墨、苯胺印刷油墨、平板油墨、孔版油墨、噴墨油墨等各種印刷油墨並利用先前用於向聚合物膜的印刷的一般的印刷方法而形成。
作為結構(2)、結構(3)中使用的基材膜1,可列舉OPP膜或PET膜等。接著層1是本發明的接著劑的硬化塗膜。作為金屬蒸鍍未拉伸膜,可使用在CPP膜實施了鋁等金屬蒸鍍的VM-CPP膜,作為金屬蒸鍍拉伸膜,可使用在OPP膜實施了鋁等金屬蒸鍍的VM-OPP膜。亦可與結構(1)同樣地於基材膜1的接著層1側的面設置印刷層。
作為結構(4)中使用的透明蒸鍍拉伸膜,可列舉於OPP膜、PET膜、尼龍膜等實施了二氧化矽或氧化鋁蒸鍍的膜。亦可以二氧化矽或氧化鋁的無機蒸鍍層的保護等為目的,使用在蒸鍍層上實施了塗佈的膜。接著層1是本發明的接著劑的硬化塗膜。密封劑膜可列舉與結構(1)相同者。亦可於透明蒸鍍拉伸膜的接著層1側的面(於使用在無機蒸鍍層上實施了塗佈者的情況下為塗佈層的接著層1側的面)設置印刷層。印刷層的形成方法與結構(1)相同。
作為結構(5)中使用的基材膜1,可列舉PET膜等。作為基材膜2,可列舉尼龍膜等。接著層1、接著層2的至少一者是本發明的接著劑的硬化塗膜。密封劑膜可列舉與結構(1)相同者。亦可與結構(1)同樣地於基材膜1的接著層1側的面設置印刷層。
作為結構(6)的基材膜1,可列舉與結構(2)、結構(3)相同者。作為金屬蒸鍍拉伸膜,可列舉於OPP膜或PET膜實施了鋁等金屬蒸鍍的VM-OPP膜或VM-PET膜。接著層1、接著層2的至少一者是本發明的接著劑的硬化塗膜。密封劑膜可列舉與結構(1)相同者。亦可與結構(1)同樣地於基材膜1的接著層1側的面設置印刷層。
作為結構(7)的基材膜1,可列舉PET膜等。作為透明蒸鍍拉伸膜,可列舉與結構(4)相同者。接著層1、接著層2的至少一者是本發明的接著劑的硬化塗膜。密封劑膜可列舉與結構(1)相同者。亦可與結構(1)同樣地於基材膜1的接著層1側的面設置印刷層。
作為結構(8)的基材膜1,可列舉PET膜等。作為金屬層,可列舉鋁箔等。接著層1、接著層2的至少一者是本發明的接著劑的硬化塗膜。密封劑膜可列舉與結構(1)相同者。亦可與結構(1)同樣地於基材膜1的接著層1側的面設置印刷層。
作為結構(9)、結構(10)的基材膜1,可列舉PET膜等。作為基材膜2,可列舉尼龍膜等。作為金屬層,可列舉鋁箔等。接著層1、接著層2、接著層3的至少一層是本發明的接著劑的硬化塗膜。密封劑膜可列舉與結構(1)相同者。亦可與結構(1)同樣地於基材膜1的接著層1側的面設置印刷層。
於本發明的積層體含有金屬蒸鍍膜、透明蒸鍍膜、金屬層中的至少一種的情況下,與金屬蒸鍍層、透明蒸鍍層、金屬層相接的接著層較佳為本發明的接著劑的硬化塗膜。
於本發明的接著劑為溶劑型的情況下,使用凹版輥等輥將本發明的接著劑塗佈於作為基材的膜材料,藉由利用烘箱等的加熱使有機溶劑揮發後,貼合另一基材,而獲得本發明的積層體。較佳為於層壓後進行老化處理。老化溫度較佳為室溫~80℃,老化時間較佳為12小時~240小時。
於本發明的接著劑為無溶劑型的情況下,於使用凹版輥等輥將預先加熱至40℃~100℃左右的本發明的接著劑塗佈於作為基材的膜材料後,立即貼合另一基材,而獲得本發明的積層體。較佳為於層壓後進行老化處理。老化溫度較佳為室溫~70℃,老化時間較佳為6小時~240小時。
於將本發明的接著劑用作接著輔助劑的情況下,使用凹版輥等輥將本發明的接著輔助劑塗佈於作為基材的膜材料,於藉由利用烘箱等的加熱使有機溶劑揮發後,利用擠出機層壓熔融後的聚合物材料,藉此獲得本發明的積層體。
接著劑的塗佈量適宜進行調整。於溶劑型接著劑的情況下,作為一例,以固體成分量成為1 g/m2
以上且10 g/m2
以下、較佳為2 g/m2
以上且5 g/m2
以下的方式調整。於無溶劑型接著劑的情況下,接著劑的塗佈量作為一例為1 g/m2
以上且5 g/m2
以下,較佳為1 g/m2
以上且3 g/m2
以下。
於將本發明的接著劑用作接著輔助劑的情況下,塗佈量作為一例為0.1 g/m2
以上且2 g/m2
以下(固體成分)。
本發明的積層體除了所述結構(1)~結構(10)以外,亦可進而含有其他膜或基材。作為其他基材,除了所述拉伸膜、未拉伸膜、透明蒸鍍膜以外,亦可使用後述的紙、木材、皮革等多孔質的基材。貼合其他基材時使用的接著劑可為本發明的接著劑,亦可不為本發明的接著劑。
作為紙,可無特別限定地使用公知的紙基材。具體而言,可使用木材紙漿等造紙用天然纖維並利用公知的抄紙機來製造,其抄紙條件並未特別規定。作為造紙用天然纖維,可列舉:針葉樹紙漿、闊葉樹紙漿等木材紙漿、馬尼拉麻紙漿、劍麻紙漿、亞麻紙漿等非木材紙漿、以及對該些紙漿實施化學改質的紙漿等。作為紙漿的種類,可使用利用硫酸鹽蒸解法、酸性/中性/鹼性亞硫酸鹽蒸解法、鈉鹽蒸解法等形成的化學紙漿、碎木漿(ground pulp)、化學碎木漿、熱磨機械漿等。
另外,亦可使用市售的各種優質紙或塗佈紙、襯里紙(backing paper)、浸漬紙、卡片紙或紙板等。另外,亦可根據需要於紙層的外表面或內表面側設置印刷層。
「其他層」亦可含有公知的添加劑或穩定劑、例如抗靜電劑、易接著塗佈劑、塑化劑、潤滑劑、抗氧化劑等。另外,為了提高與其他材料積層時的密接性,「其他層」亦可為對膜的表面進行了電暈處理、電漿處理、臭氧處理、藥品處理、溶劑處理等作為前處理者。
本發明的積層體可較佳地用作各種用途,例如食品或醫藥品、生活用品的包裝材料、或蓋材、紙吸管(paper straw)或餐巾紙、紙勺、紙盤、紙杯等紙製餐具、防壁材、屋頂材、太陽電池面板材、電池用包裝材、窗戶材料、室外鋪地材、照明保護材、汽車構件、廣告牌、張貼物等室外產業用途、射出成形的同時進行裝飾的方法等中使用的裝飾用片、洗衣用液體洗滌劑、廚房用液體洗滌劑、沐浴用液體洗滌劑、沐浴用液體肥皂、液體洗髮水、液體護髮素等的包裝材料等。
尤其是於實施蒸煮處理的情況下,若是Ny膜與鋁箔經由接著層貼合的積層體,則於該些層間容易發生剝離。因此,藉由使用本發明的接著劑將Ny膜與鋁箔貼合,可製成耐蒸煮性優異的積層體。
作為更具體的結構例,可列舉:PET膜/Ny膜/鋁箔/CPP膜、PET膜/鋁箔/Ny膜/CPP膜、Ny膜/鋁箔/Ny膜/CPP膜等,使用本發明的接著劑將Ny膜與鋁箔貼合。其他膜間可使用通用的接著劑進行貼合,亦可使用本發明的接著劑進行貼合。當然亦可於積層體的適當的位置設置印刷層。
於需要耐內容物性的情況下且於為含有鋁箔、鋁蒸鍍層、無機氧化物層等阻擋層的積層體的情況下,較佳為於設置於阻擋層與密封劑層之間的接著層中,在位於距阻擋層側最近的位置的接著層中使用本發明的接著劑。源自自密封劑側移行來的內容物的成分滯留於阻擋層的附近,因此距阻擋層最近的接著層受到內容物的影響而容易劣化。因此,藉由使用本發明的接著劑,可抑制內容物導致的接著層的劣化。
作為更具體的結構,可列舉:透明蒸鍍PET膜/基於本發明的接著層/Ny膜/密封劑膜、PET膜/鋁箔/基於本發明的接著層/密封劑膜、PET膜/鋁箔/基於本發明的接著層/PET膜/密封劑膜等。作為其他結構,包含Ny膜/基於本發明的接著層/鋁蒸鍍PET膜/密封劑膜的積層體由於耐內容物性亦優異,因此較佳。該些積層體中,基於本發明的接著層以外的接著層可使用通用的接著劑進行貼合,亦可使用本發明的接著劑進行貼合。於積層體的適當的位置設置有印刷層,但省略了記載。於耐穿刺性等需要更高強度的情況下,亦可使用透明蒸鍍Ny膜來代替鋁蒸鍍PET膜、透明蒸鍍PET膜。
<包裝材>
本發明的積層體可用作以食品或醫藥品等的保護為目的的多層包裝材料。於用作多層包裝材料的情況下,其層結構可根據內容物或使用環境、使用形態而變化。另外,亦可於本發明的包裝體中適宜設置易開封處理或再封性機構。
本發明的包裝材可使用本發明的積層體,使積層體的密封劑膜的面相向重疊後,將其周邊端部熱封並形成袋狀而獲得。作為製袋方法,可列舉如下方法:將本發明的積層體折疊或者重疊而使其內層的面(密封劑膜的面)相向並藉由例如側面密封型、兩面密封型、三面密封型、四面密封型、信封黏貼密封型、合掌黏貼密封型、帶有褶的密封型、平底密封型、方底密封型、折縫型、其他熱封型等形態對其周邊端部進行熱封。本發明的包裝材可根據內容物或使用環境、使用形態採取各種形態。亦可為自支撐性包裝材(自立袋)等。作為熱封的方法,可利用杆密封、旋轉輥密封、帶密封、脈衝密封、高頻密封、超音波密封等公知的方法進行。
於自本發明的包裝材的開口部填充內容物後可將開口部熱封來製造使用了本發明的包裝材的製品。作為所填充的內容物,例如食品可列舉:大米做的點心、豆點心、堅果類、餅乾/甜餅(biscuit/cookie)、威化點心、棉花糖、餡餅、半生蛋糕、糖果、快餐點心等點心類、麵包、快餐麵、方便麵、乾麵、通心麵、無菌包裝米飯、菜粥、粥、包裝年糕、穀類食品(cereal foods)等主食類(staple)、醬菜、煮豆、納豆、豆醬、凍豆腐、豆腐、醬醃製蘑菇、魔芋、野菜加工品、果醬類、花生奶油、色拉類、冷凍蔬菜、馬鈴薯加工品等農產加工品、火腿類、臘肉、香腸類、雞加工品、鹹牛肉類等畜產加工品、魚肉火腿/香腸、水產熟食品、魚糕、紫菜、海味小菜、乾鬆魚、鹹魚肉、熏鮭魚(smoked salmon)、芥末鱈魚子等水產加工品、桃子、桔子、菠蘿、蘋果、洋梨、櫻桃等果肉類、玉米、蘆筍、蘑菇、洋蔥、胡蘿蔔、蘿蔔、馬鈴薯等蔬菜類、漢堡牛肉餅、肉丸子、水產油炸食品、餃子、炸肉餅等為代表的冷凍家常菜、冷藏家常菜等烹飪好的食品、黃油、人造黃油、奶酪、奶油、速食乳脂粉(instant creamy powder)、育兒用調整奶粉等乳製品、液體調味料、蒸煮咖喱、寵物食品等食品類。
另外,作為非食品,亦可用作煙、一次性暖寶寶、輸液包等醫藥品、洗衣用液體洗滌劑、廚房用液體洗滌劑、沐浴用液體洗滌劑、沐浴用液體肥皂、液體洗髮水、液體護髮素、化妝水或乳液等化妝品、真空隔熱材、電池等各種包裝材料。
[實施例]
以下,列舉具體的合成例、實施例更詳細地說明本發明,但本發明並不限定於該些實施例。再者,以下的例子中,只要無特別說明,則「份」及「%」分別表示「質量份」及「質量%」。
<多元醇的合成>
(合成例1)
向包括攪拌機、氮氣導入管、斯奈德管(Snyder tube)、冷凝器的聚酯反應容器中投入乙二醇:6.4份、新戊二醇:22.3份、1,6-己二醇:9.9份、間苯二甲酸:17.3份、對苯二甲酸:21.3份、己二酸:11.9份、單體酸:0.2份、二聚酸:6.4份、三聚酸:1.3份、四聚酸:0.2份及四異丙氧基鈦10 ppm,以精餾管上部溫度不超過100℃的方式緩緩地加熱,並將內溫保持為260℃。於酸價低於規定值後,進而繼續反應1小時。減壓至30 mmHg並保持3小時,獲得固體成分酸價為0.6 mgKOH/g、羥基價為10 mgKOH/g的中間體聚酯多元醇。產率為85%。
於所獲得的中間體聚酯多元醇100質量份中加入異佛爾酮二異氰酸酯:3.6質量份,加熱至50℃~90℃並進行胺基甲酸酯化反應,直至游離的NCO基實質上消失為止,獲得羥基價為10 mgKOH/g的聚酯聚胺基甲酸酯多元醇。將其利用乙酸乙酯稀釋,對聚酯聚胺基甲酸酯多元醇(固體成分)以二月桂酸二丁基錫成為200 ppm的方式添加,獲得聚酯聚胺基甲酸酯多元醇的固體成分為60%的多元醇A-1。
(合成例2)
向包括攪拌機、氮氣導入管、斯奈德管、冷凝器的聚酯反應容器中投入乙二醇:8.2份、二乙二醇:7.3份、新戊二醇:4.5份、1,6-己二醇:18.1份、間苯二甲酸:9.1份、對苯二甲酸:27.2份、己二酸:8.2份、癸二酸:7.3份、單體酸:0.2份、二聚酸:7.4份、三聚酸:1.3份、四聚酸:0.2份及四異丙氧基鈦10 ppm,以精餾管上部溫度不超過100℃的方式緩緩地加熱,並將內溫保持為260℃。於酸價低於規定值後,進而繼續反應1小時。減壓至30 mmHg並保持3小時,獲得固體成分酸價為0.6 mgKOH/g、羥基價為14 mgKOH/g的中間體聚酯多元醇。產率為85%。
於所獲得的中間體聚酯多元醇100質量份中加入甲苯二異氰酸酯:1.4質量份,加熱至50℃~90℃並進行胺基甲酸酯化反應,直至游離的NCO基實質上消失為止,獲得羥基價為14 mgKOH/g的聚酯聚胺基甲酸酯多元醇。將其利用乙酸乙酯稀釋,於聚酯聚胺基甲酸酯多元醇(固體成分)中以二月桂酸二丁基錫成為200 ppm的方式進行添加,獲得聚酯聚胺基甲酸酯多元醇的固體成分為60%的多元醇A-2。
(合成例3)
向包括攪拌機、氮氣導入管、斯奈德管、冷凝器的聚酯反應容器中投入乙二醇:13.2份、1,6-己二醇:17.5份、間苯二甲酸:8.8份、對苯二甲酸:21.9份、己二酸:7.0份、癸二酸:7.0份、單體酸:0.6份、二聚酸:18.4份、三聚酸:3.6份、四聚酸:0.6份及四異丙氧基鈦10 ppm,以精餾管上部溫度不超過100℃的方式緩緩地加熱,並將內溫保持為260℃。於酸價低於規定值後,進而繼續反應1小時。減壓至30 mmHg並保持3小時,獲得固體成分酸價為0.7 mgKOH/g、羥基價為12 mgKOH/g的中間體聚酯多元醇。產率為84%。
於所獲得的中間體聚酯多元醇100質量份中加入六亞甲基二異氰酸酯:2.1質量份,加熱至50℃~90℃並進行胺基甲酸酯化反應,直至游離的NCO基實質上消失為止,獲得羥基價為12 mgKOH/g的聚酯聚胺基甲酸酯多元醇。將其利用乙酸乙酯稀釋,於聚酯聚胺基甲酸酯多元醇(固體成分)中以二月桂酸二丁基錫成為200 ppm的方式進行添加,獲得聚酯聚胺基甲酸酯多元醇的固體成分為60%的多元醇A-3。
(合成例4)
向包括攪拌機、氮氣導入管、斯奈德管、冷凝器的聚酯反應容器中投入乙二醇:10.6份、2-甲基-1,3-丙二醇:6.4份、1,6-己二醇:15.9份、間苯二甲酸:10.6份、對苯二甲酸:21.2份、己二酸:8.5份、壬二酸:4.2份、單體酸:0.6份、二聚酸:17.5份、三聚酸:3.3份、四聚酸:0.6份及四異丙氧基鈦10 ppm,以精餾管上部溫度不超過100℃的方式緩緩地加熱,並將內溫保持為260℃。於酸價低於規定值後,進而繼續反應1小時。減壓至30 mmHg並保持3小時,獲得固體成分酸價為0.7 mgKOH/g、羥基價為13 mgKOH/g的中間體聚酯多元醇。產率為84%。
於所獲得的中間體聚酯多元醇100質量份中加入4,4'-二苯基甲烷二異氰酸酯:0.9質量份,加熱至50℃~90℃並進行胺基甲酸酯化反應,直至游離的NCO基實質上消失為止,獲得羥基價為13 mgKOH/g的聚酯聚胺基甲酸酯多元醇。將其利用乙酸乙酯稀釋,於聚酯聚胺基甲酸酯多元醇(固體成分)中以二月桂酸二丁基錫成為200 ppm的方式進行添加,獲得聚酯聚胺基甲酸酯多元醇的固體成分為60%的多元醇A-4。
(合成例5)
向包括攪拌機、氮氣導入管、斯奈德管、冷凝器的聚酯反應容器中投入乙二醇:14.7份、2-甲基-1,3-丙二醇:5.9份、1,6-己二醇:14.7份、間苯二甲酸:29.4份、己二酸:17.6份、單體酸:0.4份、二聚酸:13.8份、三聚酸:2.9份、四聚酸:0.5份及四異丙氧基鈦10 ppm,以精餾管上部溫度不超過100℃的方式緩緩地加熱,並將內溫保持為260℃。於酸價低於規定值後,進而繼續反應1小時。減壓至30 mmHg並保持3小時,獲得固體成分酸價為0.8 mgKOH/g、羥基價為20 mgKOH/g的聚酯多元醇。產率為85%。將其利用乙酸乙酯稀釋,於聚酯多元醇(固體成分)中以二月桂酸二丁基錫成為200 ppm的方式進行添加,獲得聚酯多元醇的固體成分為60%的多元醇A-5。
(合成例6)
向包括攪拌機、氮氣導入管、斯奈德管、冷凝器的聚酯反應容器中投入乙二醇:13.9份、1,6-己二醇:23.2份、間苯二甲酸:38.6份、壬二酸:18.6份、二聚酸:0.1份、三聚酸:4.2份、四聚酸:1.1份及四異丙氧基鈦10 ppm,以精餾管上部溫度不超過100℃的方式緩緩地加熱,並將內溫保持為260℃。於酸價低於規定值後,進而繼續反應1小時。減壓至30 mmHg並保持3小時,獲得固體成分酸價為0.8 mgKOH/g、羥基價為24 mgKOH/g的聚酯多元醇。產率為85%。
於所獲得的中間體聚酯多元醇100質量份中加入甲苯二異氰酸酯:0.3質量份,加熱至50℃~90℃並進行胺基甲酸酯化反應,直至游離的NCO基實質上消失為止,獲得羥基價為24 mgKOH/g的聚酯聚胺基甲酸酯多元醇。將其利用乙酸乙酯稀釋,於聚酯聚胺基甲酸酯多元醇(固體成分)中以二月桂酸二丁基錫成為200 ppm的方式進行添加,獲得聚酯聚胺基甲酸酯多元醇的固體成分為50%的多元醇A-6。
(合成例7)
向包括攪拌機、氮氣導入管、斯奈德管、冷凝器的聚酯反應容器中投入乙二醇:12.2份、新戊二醇:15.2份、1,6-己二醇:10.1份、間苯二甲酸:16.2份、對苯二甲酸:21.8份、己二酸:24.4份及四異丙氧基鈦10 ppm,以精餾管上部溫度不超過100℃的方式緩緩地加熱,並將內溫保持為260℃。於酸價低於規定值後,進而繼續反應1小時。減壓至30 mmHg並保持3小時,獲得固體成分酸價為0.6 mgKOH/g、羥基價為10 mgKOH/g的聚酯多元醇。產率為86%。將其利用乙酸乙酯稀釋,於聚酯多元醇(固體成分)中以二月桂酸二丁基錫成為200 ppm的方式進行添加,獲得聚酯多元醇的固體成分為60%的多元醇AH-1。
(合成例8)
向包括攪拌機、氮氣導入管、斯奈德管、冷凝器的聚酯反應容器中投入乙二醇:10.3份、二乙二醇:3.6份、1,6-己二醇:25.8份、間苯二甲酸:20.7份、對苯二甲酸:15.0份、己二酸:15.0份、癸二酸:7.7份及四異丙氧基鈦10 ppm,以精餾管上部溫度不超過100℃的方式緩緩地加熱,並將內溫保持為260℃。於酸價低於規定值後,進而繼續反應1小時。減壓至30 mmHg並保持3小時,獲得固體成分酸價為0.8 mgKOH/g、羥基價為20 mgKOH/g的聚酯多元醇。產率為86%。
於所獲得的中間體聚酯多元醇100質量份中加入甲苯二異氰酸酯:1.5質量份,加熱至50℃~90℃並進行胺基甲酸酯化反應,直至游離的NCO基實質上消失為止,獲得羥基價為19 mgKOH/g的聚酯聚胺基甲酸酯多元醇。將其利用乙酸乙酯稀釋,於聚酯聚胺基甲酸酯多元醇(固體成分)中以二月桂酸二丁基錫成為200 ppm的方式進行添加,獲得聚酯聚胺基甲酸酯多元醇的固體成分為60%的多元醇AH-2。
表1、表2中示出各多元醇的固體成分羥基價、四聚酸於用於合成聚酯多元醇的單體組成物中所佔的調配量(質量%)。
[表1]
A-1 | A-2 | A-3 | A-4 | A-5 | |
羥基價(mgKOH/g) | 10 | 14 | 12 | 13 | 20 |
四聚酸調配量(質量%) | 0.23 | 0.22 | 0.62 | 0.57 | 0.52 |
[表2]
A-6 | AH-1 | AH-2 | |
羥基價(mgKOH/g) | 24 | 10 | 19 |
四聚酸調配量(質量%) | 1.14 | 0 | 0 |
<接著劑的製備>
(實施例1)
以表3中所示的調配使用多元醇A-1、聚異氰酸酯B-1(三井化學公司製造,塔克奈特(Takenate)D-110N(NB)、伸二甲苯基二異氰酸酯的三羥甲基丙烷加成物體、不揮發成分75%),製備實施例1的接著劑。
(實施例2)~(實施例6)
除了將所使用的多元醇、異氰酸酯及其調配變更為表3、表4所示者以外,與實施例1同樣地製備實施例2~實施例6的接著劑。再者,表中的聚異氰酸酯B-2為科思創(coverstro)公司製造、德斯莫杜爾(Desmodur)L75、甲苯二異氰酸酯的三羥甲基丙烷加成物體、不揮發成分75%。
(比較例1)、(比較例2)
除了將所使用的多元醇、異氰酸酯及其調配變更為表4所示者以外,與實施例1同樣地製備比較例1、比較例2的接著劑。
再者,表中的調配量是含有溶劑的值。KBM-403為3-縮水甘油氧基丙基三甲氧基矽烷(信越化學)。
<積層體的製造>
(積層體1的製造)
將實施例、比較例的接著劑分別使用棒塗機,以塗佈量為3.5 g/m2
(固體成分)的方式塗佈於厚度25 μm的PET膜,利用設定為溫度70度的乾燥機使乙酸乙酯揮發並使其乾燥。其次,將接著劑與厚度30 μm的鋁箔貼合。於40℃下進行3天老化,獲得積層體1。
(積層體2的製造)
將實施例、比較例的接著劑分別使用棒塗機,以塗佈量為3.5 g/m2
(固體成分)的方式塗佈於厚度12 μm的PET膜,利用乾燥機使乙酸乙酯揮發並使其乾燥。其次,將接著劑與厚度15 μm的拉伸尼龍膜貼合。
接著,以塗佈量為3.5 g/m2
(固體成分)的方式將實施例或比較例的接著劑塗佈於積層體的尼龍面,利用設定為溫度70度的乾燥機使乙酸乙酯揮發並使其乾燥。將接著劑與厚度9 μm的鋁箔貼合。
接著,以塗佈量為3.5 g/m2
(固體成分)的方式將實施例或比較例的接著劑塗佈於積層體的鋁箔面,利用設定為溫度70度的乾燥機使乙酸乙酯揮發並使其乾燥。將接著劑與厚度70 μm的CPP膜貼合。於40℃下進行3天老化,獲得積層體2。
(積層體3的製造)
將實施例、比較例的接著劑分別使用棒塗機,以塗佈量為3.5 g/m2
(固體成分)的方式塗佈於厚度12 μm的PET膜,利用設定為溫度70度的乾燥機使乙酸乙酯揮發並使其乾燥。其次,將接著劑與厚度9 μm的鋁箔貼合。
接著,以塗佈量為3.5 g/m2
(固體成分)的方式將實施例或比較例的接著劑塗佈於積層體的鋁箔面,利用設定為溫度70度的乾燥機使乙酸乙酯揮發並使其乾燥,將接著劑與厚度60 μm的LLDPE膜貼合。於40℃下進行3天老化,獲得積層體3。
<評價>
(常態接著力)
於25℃的環境下使用拉伸試驗機,將剝離速度設定為300 mm/min,利用T型的剝離方法測定積層體1的PET膜與鋁之間的接著強度(N/15 mm)。將結果歸納於表3、表4中。
(熱間接著力)
於100℃的環境下使用拉伸試驗機,將剝離速度設定為3 mm/min,以測定角度自由的方式測定積層體1的PET膜與鋁之間的接著強度(N/15 mm)。將結果歸納於表3、表4中。
(耐蒸煮性)
自積層體2切出試驗片,以CPP膜朝向內側的方式進行折疊,以寬度10 mm對凸起的折痕以外的三邊進行熱封。繼而,於熱封端部的任意的部位設置1.5 mm的切口(凹口),製作試驗片。將以同樣的方式製成的20個試驗片以各試驗片的凹口位於淋浴式蒸煮殺菌裝置(日阪製作所製造,弗萊波斯(flavor ace))的熱水淋浴噴嘴附近的方式設置,於135℃、30分鐘的條件下進行蒸煮處理。以如下方式評價蒸煮後的試驗片的狀態,歸納於表3、表4中。
5:長徑為3 mm以下的剝離未滿3個
4:長徑為3 mm以下的剝離為3個以上且未滿5個
3:長徑為3 mm以下的剝離為5個以上且未滿10個
2:長徑為3 mm以下的剝離為10個以上,或超過3 mm的剝離未滿5個
1:長徑超過3 mm的剝離為5個以上
(耐內容物性)
使用積層體3,以LLDPE膜朝向內側的方式進行折疊,以與熱封後的內容物的接觸面積為200 cm2
的方式製成袋(pouch)。於填充d-檸檬烯(東京化成工業製造):20 ml後進行熱封並密閉,於40℃下靜置1周。以如下方式評價恢復至室溫的袋的鋁箔與LLDPE膜之間的狀態,歸納於表3、表4中。
5:無剝離
4:僅於凸起的折痕附近觀察到未滿10 mm(長邊)的剝離
3:僅於凸起的折痕附近觀察到10 mm以上(長邊)的剝離
2:於一半左右的袋中觀察到了剝離
1:於袋的整個面觀察到了剝離
[表3]
實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | ||
多元醇A-1 | 12 | |||||
多元醇A-2 | 10 | |||||
多元醇A-3 | 12 | |||||
多元醇A-4 | 10 | |||||
多元醇A-5 | 7 | |||||
聚異氰酸酯B-1 | 1 | 1 | ||||
聚異氰酸酯B-2 | 1 | 1 | 1 | |||
NCO/OH | 2.1 | 2.2 | 2.1 | 2.3 | 1.8 | |
評價結果 | ||||||
耐熱性 | 常態接著強度 | 4.2 | 4.3 | 4.5 | 4.5 | 4.1 |
熱接著強度 | 2.8 | 3.2 | 3.3 | 3.2 | 2.4 | |
耐蒸煮性 | 4 | 4 | 5 | 4 | 4 | |
耐內容物性 | 3 | 4 | 4 | 4 | 3 |
[表4]
實施例6 | 實施例7 | 比較例1 | 比較例2 | ||
多元醇A-5 | 7 | ||||
多元醇A-6 | 9 | ||||
多元醇AH-1 | 12 | ||||
多元醇AH-2 | 12 | ||||
聚異氰酸酯B-1 | 1 | 1 | |||
聚異氰酸酯B-2 | 1 | 1 | |||
KBM-403 | 0.042 | ||||
NCO/OH | 1.8 | 1.7 | 2.5 | 2.5 | |
評價結果 | |||||
耐熱性 | 常態接著強度 | 4.2 | 4.5 | 3.8 | 4.3 |
熱接著強度 | 2.9 | 3.5 | 1.9 | 2.1 | |
耐蒸煮性 | 4 | 5 | 1 | 2 | |
耐內容物性 | 3 | 5 | 1 | 1 |
如根據表3、表4明確般,本發明的接著劑是常態接著強度、熱接著強度、耐蒸煮性、耐內容物性優異者。另一方面,與實施例的接著劑相比,比較例的接著劑是耐蒸煮性、耐內容物性差者。
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Claims (12)
- 一種接著劑,其特徵在於包含: 含有聚異氰酸酯化合物(A1)的聚異氰酸酯組成物(A);以及 含有聚酯多元醇(B1)的多元醇組成物(B), 所述聚酯多元醇(B1)是包含多元羧酸與多元醇的單體組成物的反應生成物,所述多元羧酸包含四聚酸。
- 如請求項1所述的接著劑,其中所述四聚酸於所述單體組成物中所佔的調配量為0.1質量%以上且4.0質量%以下。
- 如請求項1或請求項2所述的接著劑,其中所述單體組成物含有官能基間的最短的亞甲基鏈的碳原子數為6以上且20以下的化合物(b)。
- 如請求項1至請求項3中任一項所述的接著劑,其中所述化合物(b)於所述單體組成物中所佔的調配量為0.1質量%~35質量%。
- 如請求項1至請求項4中任一項所述的接著劑,其中所述單體組成物含有選自均苯四甲酸、均苯四甲酸酐、山梨糖醇、季戊四醇、二季戊四醇中的至少一種。
- 如請求項1至請求項5中任一項所述的接著劑,其中所述聚酯多元醇(B1)是含有所述多元羧酸、所述多元醇及異氰酸酯化合物的組成物的反應生成物。
- 一種積層體,具有: 第一基材; 第二基材;以及 接著層,將所述第一基材與所述第二基材貼合, 所述接著層是如請求項1至請求項6中任一項所述的接著劑的硬化物。
- 如請求項7所述的積層體,其中所述第一基材包含鋁,所述第二基材包含尼龍。
- 如請求項7所述的積層體,其中所述第一基材為阻擋層。
- 一種包裝材,包含如請求項7至請求項9中任一項所述的積層體。
- 一種蒸煮用包裝材,包含如請求項8所述的積層體。
- 一種非食品用包裝材,包含如請求項9所述的積層體。
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JP (1) | JP7036293B1 (zh) |
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