CN101146883B - 用于层合材料的胶粘剂 - Google Patents
用于层合材料的胶粘剂 Download PDFInfo
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- CN101146883B CN101146883B CN2006800093156A CN200680009315A CN101146883B CN 101146883 B CN101146883 B CN 101146883B CN 2006800093156 A CN2006800093156 A CN 2006800093156A CN 200680009315 A CN200680009315 A CN 200680009315A CN 101146883 B CN101146883 B CN 101146883B
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- CN
- China
- Prior art keywords
- polyester polyol
- acid
- laminate
- tackiness agent
- molecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 28
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Abstract
本发明提供一种用于层合材料的胶粘剂,所述胶粘剂在保持优良的耐内容物性能的同时,还具有高的初始粘接力,生产效率高,作业性能良好。本发明的用于层合材料的胶粘剂至少由主剂溶液和异氰酸酯固化剂组成。该主剂溶液含有聚氨酯树脂,硅烷类偶联剂及有机溶剂,所述聚氨酯树脂是通过令化合物(A),(B),(C)和(D)以质量比为(A)/(B)=95/5~75/25的比例反应而获得,其中,(A)为分子中含有芳环且分子末端实质上为羟基的聚酯多元醇,(B)为分子中不含芳环的聚酯多元醇,(C)为二羟甲基链烷酸,(D)为有机聚异氰酸酯。
Description
技术领域
本发明涉及一种胶粘剂,尤其涉及适合于金属等的薄膜的干性层合材料的胶粘剂。
背景技术
最近,出于强度高、对商品的保护性能好、包装时的作业适应性强、包装的宣传效果好、因塑性材料的大量、廉价的供给使得包装成本降低等理由,复合软包装作为包装方法获得显著的发展。
作为用于这种薄膜层合材料的胶粘剂,基于粘接性能以及耐寒、耐热性能优越,对于各种塑料、金属箔等基材的适应范围广等的考虑,通常,由具有羟基等活性氢基团的主剂和具有异氰酸酯基的固化剂组成的双液型聚氨酯系的胶粘剂成为主流。
但是,目前用于层合材料的双液型聚氨酯系胶粘剂,由于在粘接之后胶粘剂的固化反应进行得非常慢,需要有一个称为所谓“老化”(aging)的促进固化的工序。具体地说,进行层合加工的薄膜需要在35~60℃的保温室中保存3~5天左右,通过老化使胶粘剂固化。此时,因老化条件不同,胶粘剂的固化程度会发生变化,有时会影响层合薄膜的粘接强度,当老化不够充分时,有时会因胶粘剂固化不良引起脱层(层剥离)。尤其是脂肪族聚氨酯系胶粘剂,其固化反应需要相当长的时间。因此,这样的老化工序在于性层合过程中是不可缺少的工序,需要老化用保温室设置的设备投资,以及此后用于保温的实际费用等。
为了解决这些问题,缩短固化时间进而提高生产效率,及为了改善涂胶和粘接的性能,专利文献1提出一种含有(a)二甘醇系的聚酯聚氨酯多元醇、(b)含有羧基的芳香族系聚酯多元醇和(c)含有聚异氰酸酯的干性层合用的胶粘剂。由于该(b)含有羧基的芳香族系聚酯多元醇为令芳香族多元羧酸酐与聚酯多元醇反应所得,因此,聚酯多元醇分子的末端就变成了羧基。其结果, 采用专利文献1的干性层合用的胶粘剂制造的层合薄膜包装材料,在装入食品或药品等内容物,用于进行如煮沸、蒸煮等的高温处理的用途时,虽然可以提高其粘接性能、耐热水性能、耐酸性能等的耐内容物的性能,但是,薄膜经高温处理后的外观(剥离)却明显变差。
专利文献1:特开2000-154365号公报
发明内容
本发明就是为解决上述先有技术所存在的问题而提出来的,其目的在于,提供一种用于层合材料的胶粘剂,所述胶粘剂在保持优良的耐内容物性能的同时,还具有高的初始粘接力,生产效率高,作业性能良好。
本发明者发现:同时并用(A)分子中含有芳环的刚性聚酯多元醇和(B)除此之外的柔性聚酯多元醇作为主剂的主要组成成分的聚氨酯树脂的原料,且将羧基导入树脂中的特定部位,由此,发现解决上述课题的途径,最终完成本发明。
即,为了达到上述目的,本发明提出以下技术方案(1)~(3)。
(1)一种用于层合材料的胶粘剂,其特征在于:
所述胶粘剂至少由主剂溶液和异氰酸酯固化剂组成,所述主剂溶液含有聚氨酯树脂,硅烷类偶联剂以及有机溶剂,所述聚氨酯树脂由使得下述的(A),(B),(C)及(D)以质量比为(A)/(B)=95/5~75/25的比例反应而获得:
(A)分子中含有芳环、且分子末端实质上为羟基的聚酯多元醇,
(B)分子中不含芳环的聚酯多元醇,
(C)二羟甲基链烷酸,
(D)有机聚异氰酸酯。
(2)在(1)所述的用于层合材料的胶粘剂中,其特征在于:
(A)和(B)二者在常温下均为粘稠液体。
(3)在(1)或(2)所述的用于层合材料的胶粘剂中,其特征在于:
(C)为二羟甲基丁酸。
下面说明本发明的效果。
采用本发明的用于层合材料的胶粘剂制造的塑料薄膜或金属箔等的层合薄膜,在维持优良的耐内容物性能的同时,初始剥离粘接强度及常态下剥离粘接强度等的粘接性能也很优异。在煮沸处理或蒸煮处理后,层合薄膜的外观未见脱层等异常,可以确认保持实用意义上的粘接强度。其结果,在制造薄膜时,能够防止隧道效应或薄膜偏移,具有良好的生产性和作业性。
由此,根据本发明,可大幅度提高层合薄膜的生产效率和作业性,降低成本和缩短交货期。
具体实施方式
下面详细说明本发明的最佳实施形态。
本发明的用于层合材料(lamination)的胶粘剂至少由主剂溶液和异氰酸酯固化剂组成。
本发明中的主剂溶液含有聚氨酯树脂、硅烷类偶联剂及有机溶剂。
主剂溶液中的聚氨酯树脂系令(A)分子中含有芳环、且分子末端实质上为羟基的聚酯多元醇、(B)分子中不含芳环的聚酯多元醇、(C)二羟甲基链烷酸、(D)有机聚异氰酸酯反应而得到。
再有,(A)分子中含有芳环、且分子末端实质上为羟基的聚酯多元醇与(B)分子中不含芳环的聚酯多元醇的质量比(A)/(B)=95/5~75/25。
(A)聚酯多元醇分子中虽含有芳环,但分子末端实质上是羟基(即,分子末端实质上不存在羧基)。具体来说,以聚酯多元醇的酸价≤1mg KOH/g为宜。
作为(A)聚酯多元醇,具体地可例举:由例如对苯二甲酸、间苯二甲酸等的芳香族羧酸、其酸酯、酸酐等与多元醇经脱水缩合反应得到的聚酯多元醇;或者,由上述的芳香族羧酸、其酸酯、酸酐等与丁二酸、己二酸、癸二酸、壬二酸、六氢化对苯二甲酸、六氢化间苯二甲酸等的芳香族以外的羧酸、它们的酸酯、酸酐等与多元醇经脱水缩合反应得到的聚酯多元醇;或者,由上述的芳香族羧酸、其酸酯、酸酐等与多元醇经脱水缩合反应得到的聚酯多元醇与除此之外的聚酯多元醇的混合物。作为这样的(除此之外)的聚酯多元醇可举出:经芳香族以外的羧酸、它们的酸酯、酸酐等与多元醇经脱水缩合反应得到的聚酯多元醇,及ε-己内酰胺,烷基置换的ε-己内酯、δ-戊内酯,烷基置换的δ-戊内酯等的环状酯(即,内酯)单体的开环聚合反应得到的内酯系聚酯多元醇等。
这些化合物中,较好的是,以上述芳香族二羧酸、其酸酯、酸酐等以及芳香族以外的二羧酸、它们的酸酯、酸酐等与多元醇经脱水缩合反应得到的聚酯多元醇。
作为上述多元醇,可例举:乙二醇,1,3-丙二醇,1,2-丙二醇,1,4-丁二醇,1,5-戊二醇,1,6-己二醇,3-甲基-1,5-戊二醇,2-丁基-2-乙基-1,3-丙二醇,新戊二醇,1,8-辛二醇,1,9-壬二醇,二甘醇,1,4-环己二醇,1,4-环己烷二甲醇,二聚体酸二醇,三羟甲基丙烷,丙三醇,己三醇,或它们的环氧乙烷或环氧丙烷的加成物等的二元醇或三元醇。
这些聚酯多元醇可以单独使用,也可以将两种或两种以上的多元醇混合使用。
从是否容易得到(价廉,而且是通常的工业生产的产品)来考虑,理想的是在芳环上引入酸性成分(具体地说,即上述芳香族二羧酸、其酸酯、酸酐等)的聚酯多元醇。
(B)聚酯多元醇分子中不含有芳环,具体地可例举上述芳香族以外的二羧酸、它们的酸酯、酸酐等与(芳香族以外的)多元醇经脱水缩聚反应所得到的聚酯多元醇,上述环状酯(即,内酯)单体的开环聚合反应得到的内酯系聚酯多元醇等。
这些聚酯多元醇可以单独使用,也可以将两种或两种以上的多元醇混合使用。
其中,理想的是,上述芳香族以外的二羧酸、它们的酸酯、酸酐等与(芳香族以外的)多元醇经脱水缩聚反应所得到的聚酯多元醇。
这些(A)(B)聚酯多元醇以常温下都是粘稠液体为宜。
这些(A)(B)聚酯多元醇的分子量都以200~20,000为宜,更适宜的分子量为400~10,000。如分子量太大,则氨酯基等的导入量减少,导致聚氨酯树脂的高韧性和内聚力都会减小,不能令人满意。如分子量过小,则聚氨酯树脂有发脆的倾向,也不宜使用。
作为(C)二羟甲基链烷酸,可例举:二羟甲基丙酸,二羟甲基丁酸,二羟甲基戊酸,二羟甲基己酸,二羟甲基庚酸,二羟甲基辛酸,二羟甲基壬酸,二羟甲基癸酸。
这些二羟基链烷酸可以单独使用,也可以将两种或两种以上的多元醇混合使用。
其中,较好的是二羟基丁酸。
作为(D)有机聚异氰酸酯,除了有机聚异氰酸酯单体外,还可列举含有机聚异氰酸酯改性体的有机聚异氰酸酯化合物等。
例如可以列举:2,4-甲苯二异氰酸酯,2,6-甲苯二异氰酸酯,二甲苯-1,4-二异氰酸酯,二甲苯-1,3-二异氰酸酯,二苯甲烷-4,4’-二异氰酸酯,二苯甲烷-2,4’-二异氰酸酯,4,4’-二异氰酸二苯醚酯,4,4’-二异氰酸2-硝基苯酯,2,2’-二苯丙烷-4,4’-二异氰酸酯,3,3’-二甲基二苯基甲烷-4,4’-二异氰酸酯,4,4’-二苯丙烷二异氰酸酯,间-苯二异氰酸酯,对-苯二异氰酸酯,亚萘基-1,4-二异氰酸酯,亚萘基-1,5-二异氰酸酯,3,3’-二甲氧基4,4’-二异氰酸酯联苯等的芳香族二异氰酸酯,二异氰酸四亚甲酯,二异氰酸六亚甲酯,二异氰酸赖氨酸酯等脂肪族二异氰酸酯,异佛尔酮二异氰酸酯,氢化甲苯二异氰酸酯,二异氰酸氢化二甲苯酯,氢化二苯甲烷二异氰酸酯,二异氰酸四甲代二甲苯酯等脂环族二异氰酸酯等的二异氰酸酯,以及上述二异氰酸酯的缩二脲体,二聚体,三聚体,二聚·三聚体,脲基亚胺改性体,还有由双官能以上的多元醇等与上述二异氰酸酯或其多聚体的反应所得到的聚异氰酸酯的加合体等的有机异氰酸酯的改性体等。
这些化合物可以单独使用,也可以将两种或两种以上混合使用。
在这些化合物中,优选脂肪族二异氰酸酯和/或脂环族二异氰酸酯,尤其优选脂环族二异氰酸酯。
主剂溶液中的聚氨酯是由(A)分子中含有芳环、且分子末端实质上为羟基的聚酯多元醇、(B)分子中不含芳环的聚酯多元醇、(C)二羟甲基链烷酸、(D)有机聚异氰酸酯,在100℃的温度下,以(A)/(B)=95/5~75/25(质量比),优选异氰酸基的当量/羟基的当量=0.50/1.00~0.98/1.00条件下,使各成分均一混合反应而制得。
所得到的聚氨酯树脂的数均分子量以3,000~60,000为宜,更理想的是10,000~40,000。
作为反应装置,只要能够完成上述反应的都可以使用。例如,可以举出带搅拌装置的反应釜或捏和机、单螺杆或多螺杆挤出反应机等的混合混炼装置。
为了加速反应的进行,可以采用在聚氨酯或聚脲制造过程中常用的二月桂酸二丁基锡等的金属触媒或三乙胺等的叔胺类触媒作为催化剂。
作为主剂溶液中的硅烷类偶联剂,可以例举,如γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷,乙烯基三乙氧基硅烷等乙烯基硅烷化合物,如β-(3,4-环氧环己基)乙基三甲氧基硅烷,γ-环氧丙氧基丙基三甲氧基硅烷等环氧硅烷化合物,如γ-氨丙基三乙氧基硅烷,N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷等氨基硅烷化合物,如γ-巯醇基丙基三甲氧基硅烷等巯基硅烷化合物。
这些化合物可以单独使用,也可以将两种或两种以上混合使用。
其中,较好的是,环氧硅烷化合物,更理想的是γ-环氧丙氧基丙基三甲氧基硅烷。
硅烷类偶联剂的配入量,根据偶联剂对基材薄膜的覆盖面积和被覆盖率以及粘接性能看来,对于每100质量份的聚氨酯树脂的固体分,以0.05~10.00质量份为宜,更理想的是0.1~5.00质量份。
作为主剂溶液中的有机溶剂,可以例举聚氨酯工业常用的惰性有机溶剂,如,甲苯、二甲苯等的芳烃系溶剂,如乙酸乙酯、乙酸丁酯等的酯系溶剂,如甲乙酮、环己酮等的酮系溶剂,如乙二醇乙醚乙酸酯、丙二醇甲醚乙酸酯、乙基-3-乙氧基丙酸酯等的乙二醇醚酯系溶剂,如四氢呋喃、二噁烷等的醚系溶剂,如N,N-二甲基甲酰胺、二甲基乙酰酰胺、N-甲基吡咯烷酮、糠醛等的极性溶剂。
这些溶剂可以单独使用,也可以将两种或两种以上混合使用。
作为本发明中的异氰酸酯固化剂,虽然可以使用上述的化合物等作为(D)有机聚异氰酸酯,但具体地说,日本聚氨酯工業株式会社制造的CoronateL,Coronate 3041,Coronate HL,Coronate HX等的有机聚异氰酸酯的改性体是合适的固化剂。
异氰酸酯固化剂的配入量,对于每100质量份的聚氨酯树脂的固体分,换算成固体分,以1~30质量份为宜,更理想的是3~15质量份。
在本发明中,还可以并用催化剂及泡沫稳定剂。虽然它们可以与异氰酸酯固化剂配合在一起使用,但最好与主剂溶液配合在一起使用。
作为催化剂,具体可以例举:如二月桂酸二丁基锡、二月桂酸二辛基锡、辛酸亚锡等的锡系触媒,如三亚乙基二胺、三乙胺、N,N,N’,N’-四甲基丙临二胺、N,N,N’,N’-四(2-羟基丙基)乙二胺、N-甲基吗啉、1,2-二甲基咪唑、1,5-重氮-二环(4,3,0)壬烷-5,1,8-重氮二环(5,4,0)-十一碳烯-7(DBU),这些胺系触媒的硼烷盐,DBU酚盐,DBU辛酸盐,DBU碳酸盐等胺盐系触媒,如环烷酸镁、环烷酸铅、醋酸钾等的羧酸盐类,如三乙膦、三苄基膦等的三烷基膦类、甲醇钠等醇盐类,锌系金属触媒等。
催化剂的配入量,对于聚氨酯树脂的固形分,以0.001~5.00质量%为宜,更好地是0.01~2.00质量%。
作为泡沫稳定剂可以例举:含有必要数量的如环氧乙烷、环氧丙烷、环氧丁烷(优选环氧乙烷)那样的烯化氧的聚乙二醇醚与含有至少一个活性氢原子的有机化合物经缩聚得到的化合物。作为这种含有至少一个活性氢原子的有机化合物,可以举出醇、酚、硫醇、伯胺或仲胺、碳酸或磺酸,它们的酰胺非离子表面活性剂,具有一个以上的烷基取代基的酚系化合物的聚醚衍生物等。
还可以列举普路罗尼克(Pluronic,商名)型表面活性剂。这是将如环氧丁烷、四氢吡喃、氧化苯乙烯、环己烯化氧、环氧丙烷或它们的混合物那样的1,2-烯化氧或取代烯化氧在碱触媒存在下发生聚合反应,制成对应的不溶于水的聚亚烷基二醇,在同样条件下与必要摩尔数的环氧乙烷缩聚得到的非离子表面活性剂。
还可以举出将如三聚丙烯、四聚丙烯、五聚丙烯、双三聚丁烯、三聚异丁烯、亚丙基异丁烯及三聚丁烯等那样的多烯烃与一氧化碳和氢经过催化反应生成的醛还原得到的醇与必要摩尔数的环氧乙烷反应得到的非离子表面活性剂。
作为理想的泡沫稳定剂的一个例子,可以举出有机聚硅氧烷。
泡沫稳定剂的配入量以对于聚氨酯树脂的固形分为3质量%以下为宜。
作为本发明中用于层合的薄膜可以列举:如铝,铜等的金属箔,如延伸性的聚丙烯,无延伸性的聚丙烯(以下略称为CPP),聚酯(以下略称为PET),尼龙(以下略称为NY),线性低密度聚乙烯(以下略称为LLDPE),低密度聚乙烯,高密度聚乙烯,乙烯-醋酸乙烯酯共聚物,聚乙烯醇,乙烯-乙烯醇共聚物,聚苯乙烯,聚碳酸酯,聚偏氯乙烯,聚氯乙烯等的塑料薄膜,纸等,以及在这些薄膜,纸上涂布聚合物涂层的薄膜。
这些薄膜在进行层合之前,最好进行电晕放电等适当的表面处理以提高粘接力。
涂布过高聚物的薄膜有可能会产生气泡,发生粘接力下降的问题,所以事先需要考虑涂布高聚物的种类,涂布量和表面特性等。
本发明的用于层合的胶粘剂可以用在干性层合,热熔层合,挤出层合等熟知的层合方法中。另外,已层合的薄膜可以在常温下(最好40~50℃)用一定的时间(最好48小时以内)老化,完成固化反应。
根据上述本发明,不仅可以将两张薄膜层合起来,还可以制造出由三张或三张以上的薄膜层合起来的层合体。
实施例
以下,详细说明本发明的实施例,但本发明的解释并非仅限于实施例。如无特别预先说明,合成例,实施例和比较例中的%都指的是“质量%”。
[分子中含有芳环、且分子末端实质上为羟基的聚酯多元醇的合成]
合成例1
将25克乙二醇和400克新戊基乙二醇加入置有搅拌器、温度计、氮封管和冷却器的反应器内,于120℃下溶解后,加入269克己二酸和306克间苯二甲酸,常压下,于220℃进行酯化反应。在馏出所定量的水之后,加入0.03克的钛酸四丁酯,5小时内从常压缓慢减压至2.7kPa abs(绝压)。其后,在220℃下进行酯交换反应5个小时,得到酸价为0.4mg KOH/g、羟基价为56.1mgKOH/g、数均分子量为2,000、常温下为粘稠液体的聚酯多元醇。
该聚酯多元醇称为A-1。
[分子中不含芳环的聚酯多元醇的合成]
合成例2
将148克乙二醇和148克二甘醇加入与合成例1同样的反应器内,于120℃下溶解后,加入611克己二酸,常压下于220℃进行酯化反应。在馏出所定量的水之后,加入0.03克的钛酸四丁酯,5小时内从常压缓慢减压至2.7kPa abs(绝压)。其后,在220℃下进行酯交换反应5个小时,得到酸价为0.3mg KOH/g、羟基价为56.1mg KOH/g、数均分子量为2,000、常温下为粘稠液体的聚酯多元醇。
该聚酯多元醇称为A-2。
实施例1~7及比较例1~4
[聚氨酯树脂的合成]
将聚酯多元醇A-1,A-2和丁酸二羟甲酯溶于乙酸乙酯中,其中加入催化剂(二月桂酸二辛基锡)。再往其中加入异佛尔酮二异氰酸酯使反应进行,制得不挥发份80质量%的聚氨酯树脂溶液。
[主剂溶液的制备]
往所制得的该聚氨酯树脂溶液中,配入乙酸乙酯、硅烷类偶联剂(信越化学工業株式会社生产的KBM-403,γ-环氧丙氧基丙基三甲氧基硅烷)和消泡剂(BYK JAPAN公司生产的BYK-354),配制成不挥发份60质量%的用于层合的胶粘剂的主剂溶液。
[用于层合的胶粘剂的制备]
用配制的该主剂溶液和异氰酸酯固化剂(日本聚氨酯工業株式会社生产的Coronate HX,二异氰酸六亚甲酯的三聚体,异氰酸酯含量21.3%,固形分100%),按下述方法制造层合薄膜,测试其性能。
结果汇集在表1和表2中。
[层合薄膜的制造]
按照下述条件,将实施例1~7或比较例1~4的胶粘剂涂布在第一层塑料薄膜上干燥后,用压料辊(niproll)将第二层塑料薄膜贴合到该第一层塑料薄膜上,老化,制得两层的层合薄膜。使用该两层的层合薄膜,再在其上涂布胶粘剂使其干燥后,用压料辊贴合第三层塑料薄膜,老化,制得三层的层合薄膜。
胶粘剂的固形分:30%(用乙酸乙酯稀释)
层合薄膜的组成:15μNY/60μLLDPE
12μPET/7μAl/70μCPP
胶粘剂的涂布量:3.5g/m2(干燥后)
干燥条件:80℃×5秒钟
老化条件:40℃×30小时
[层合薄膜的性能测试]
按照下述条件对层合薄膜进行评价。结果汇集在表1和表2中。
初始剥离粘接强度:在25℃下贴合后立即进行T型剥离试验
依照JIS K 6854(日本工业标准)
拉伸速度:300mm/分钟
常态下剥离粘接强度:贴合后在40℃下经过30小时后进行T型剥离试验
依照JIS K 6854
拉伸速度:300mm/分钟
耐内容物性能(蒸煮处理):将由PET/Al/CPP组成的层合薄膜在40℃下经过30小时的老化处理后,紧接着热封做成袋子,装入食醋/食用油/蕃茄酱(1/1/1质量比)的混合物。然后,在135℃下经过30分钟的蒸汽蒸煮处理,测定Al/CPP之间的剥离粘接强度。
耐内容物性能(煮沸处理):将NY/LLDPE组成的层合薄膜在40℃下经过30小时的老化处理后,紧接着热封做成袋子,装入水/食用油(1/9质量比)的混合物。然后,在100℃下经过30分钟的煮沸处理,测定NY/LLDPE之间的剥离粘接强度。
表1
表2
注1)聚酯多元醇A-1:
己二酸/间苯二甲酸/乙二醇/新戊基乙二醇=269/306/25/400
2)聚酯多元醇A-2:
己二酸/乙二醇/二甘醇=611/148/241
3)表中“破坏”为“材料破坏”之略。
蒸煮用的薄膜的组成例如为PET/Al/CPP时,从不发生落锤试验时袋子破裂、长期保存时剥离等这样的不合适状况角度考虑,蒸煮处理后的粘接强度至少需要大于5.0N/15mm。
煮沸用的薄膜的组成例如为NY/LLDPE时,根据与蒸煮同样的观点考虑,至少需要同等程度的粘接强度。
比较例5
按照以下所示的工序制造用于层合的胶粘剂,采用与实施例1~7以及比较例1~4的同样方法,对紧接着蒸煮处理后的外观进行评价。
[聚酯多元醇XA的制造]
用548.5克间苯二甲酸和839.2克二甘醇,在氮气流保护下,于180~220℃的温度下进行酯化反应。接着,在馏出所定量的水之后,加入482.5克己二酸,在180~220℃的温度下进行酯化反应,得到数均分子量约2,000的聚酯多元醇XA。将该全部的量溶解于400.0克醋酸乙酯,形成固形分为80%的溶液。
[聚酯多元醇XB的制造]
用529.4克的间苯二甲酸、128.8克的乙二醇和302.4克的新戊基乙二醇,在氮气流保护下,于180~220℃的温度下进行酯化反应。接着,在馏出所定量的水之后加入214.8克的癸二酸,在180~220℃的温度下进行酯化反应,得到数均分子量约3,000的聚酯多元醇XB。将该多元醇全量溶解于428.6克的醋酸乙酯,形成固形分为70%的溶液。
[聚氨酯树脂溶液XC的制造]
将160.74克的聚酯多元醇XA和459.26克的聚酯多元醇XB在氮气氛保护下,于50℃时混合均匀后,加入49.83克的异佛尔酮二异氰酸酯,在77~80℃温度下进行三小时尿烷化反应。然后加入0.10克的Stanoct(锡系尿烷化反应催化剂,吉富精密化学公司生产),再继续进行尿烷化反应三小时。尿烷化反应结束后,冷却至70℃,加入醋酸乙酯330.07克,得到固形分为50%的聚氨酯树脂溶液XC。所得到的聚氨酯树脂的数均分子量约为10,000。
[聚酯多元醇XD的制造]
用324.88克的间苯二甲酸、106.16克的乙二醇、102.61克的新戊基乙二醇、151.34克的1,6-己二醇,0.20克的醋酸锌,在氮气流保护下,于180~220℃的温度下进行酯化反应。在馏出所定量的水之后,加入95.24克己二酸,在220~230℃的温度下进行酯化反应。缓慢减压,在220~230℃的温度下进行反应60分钟后,在220~230℃的温度,1~2Torr压力下进行酯化反应4小时,得到数均分子量约为5,500的聚酯多元醇XD’。对此加入0.96克的偏苯三酸酐,令在140~150℃的温度下反应后溶解在600.96克的醋酸乙酯中,形成固形分为50%的溶液,得到含羧基的聚酯多元醇XD。所得到的聚酯多元醇XD末端的羟基的约2摩尔%是与偏苯三酸酐反应的产物。
[异氰酸酯固化剂XE的制造]
将50克Takenate A-10(苯二亚甲基二异氰酸酯的三羟甲基丙烷加成物,武田薬品工業株式会社生产)和50克Takenate A-40(异佛尔酮二异氰酸酯的三羟甲基丙烷加成物,武田薬品工業株式会社生产)在氮气气氛中于50℃的温度下均匀混合,得到异氰酸酯固化剂XE。
[层合材料用胶粘剂的制备和层合薄膜的制造]
用100克的聚氨酯树脂溶液XC,100克的聚酯多元醇XD,23.5克的异氰酸酯固化剂XE以及0.5克的硅烷类偶联剂(信越化学工業株式会社生产的KBM-403),采用与实施例1~7和比较例1~4同样的方法制造层合薄膜。
[紧接着蒸煮处理后的外观评价]
用该层合薄膜,采用与实施例1~7和比较例1~4同样的方法进行处理,在确认紧接着该处理之后的外观时,确认是否有剥离发生。
采用本发明的层合材料用胶粘剂制造的层合薄膜,可以广泛用于食品包装和换装容器包装等的用途。
上面参照附图说明了本发明的实施例,但本发明并不局限于上述实施例。在本发明技术思想范围内可以作种种变更,它们都属于本发明的保护范围。
Claims (3)
1.一种用于层合材料的胶粘剂,其特征在于:
所述胶粘剂至少由主剂溶液和异氰酸酯固化剂组成,所述主剂溶液含有聚氨酯树脂,硅烷类偶联剂以及有机溶剂,所述聚氨酯树脂由使得下述的(A),(B),(C)及(D)以质量比为(A)/(B)=95/5~85/15的比例反应而获得:
(A)分子中含有芳环、且分子末端实质上为羟基的聚酯多元醇,
(B)分子中不含芳环的聚酯多元醇,
(C)二羟甲基链烷酸,
(D)有机聚异氰酸酯。
2.如权利要求1记载的用于层合材料的胶粘剂,其特征在于:
(A)和(B)二者在常温下均为粘稠液体。
3.如权利要求1或2记载的用于层合材料的胶粘剂,其特征在于:
(C)为二羟甲基丁酸。
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KR101136598B1 (ko) * | 2009-12-30 | 2012-04-18 | 조광페인트주식회사 | 편조용 수용성 폴리머 조성물 및 이를 포함하는 도료 조성물 |
JP5707866B2 (ja) * | 2010-10-29 | 2015-04-30 | 大日本印刷株式会社 | バリア性積層体 |
CN102140304B (zh) * | 2010-12-28 | 2013-04-17 | 东莞市普赛达密封粘胶有限公司 | 一种聚氨酯密封胶用底涂剂及其制备方法 |
KR101429578B1 (ko) * | 2011-04-22 | 2014-08-12 | 디아이씨 가부시끼가이샤 | 수지 조성물, 2액형 라미네이트용 접착제, 적층 필름 및 태양 전지의 백 시트 |
CN103013419B (zh) * | 2013-01-11 | 2014-04-02 | 南通高盟新材料有限公司 | 银行卡复合用粘合剂及其制备方法 |
JP6307601B2 (ja) | 2013-10-15 | 2018-04-04 | ローム アンド ハース カンパニーRohm And Haas Company | 箔を結合する方法 |
BR112016008310B1 (pt) * | 2013-10-15 | 2021-07-27 | Rohm And Haas Company | Método de ligação a folha metálica |
CN104232004B (zh) * | 2014-09-26 | 2017-05-17 | 南京汇鑫光电材料有限公司 | 一种聚氨酯压敏胶组合物及其制备方法和应用 |
CN104479611B (zh) * | 2014-11-28 | 2016-04-27 | 佛山市永发贸易有限公司 | 一种适合彩钢板覆膜粘贴的耐候性胶水 |
JP6278166B1 (ja) * | 2016-06-23 | 2018-02-14 | Dic株式会社 | ウレタン系接着剤、ウレタン系接着剤用ポリオール組成物、ウレタン系接着剤用ポリイソシアネート組成物、前記ウレタン系接着剤の硬化物、及び積層フィルム |
CN106701004A (zh) * | 2016-12-28 | 2017-05-24 | 江苏康耐特光学有限公司 | 偏光镜片用的双组份聚氨酯胶黏剂及制造方法 |
KR101874301B1 (ko) * | 2017-01-02 | 2018-07-04 | (주)노루페인트 | 핫멜트 접착제용 폴리우레탄 수지 및 이를 포함하는 2액형 폴리우레탄 핫멜트 접착제 및 핫멜트 접착제용 폴리우레탄 수지의 제조방법. |
CN109705309A (zh) * | 2018-12-07 | 2019-05-03 | 旭川化学(苏州)有限公司 | 一种尼丝纺织物层压用耐水洗湿气反应型聚氨酯树脂及其制备方法 |
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